Asim K. Das Vol 6 The Alchemy Library

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Fundamental Concepts of Inorganic Chemistry
Contents of Volumes 1-7
Volume 1
Atomic Structure; Wave Mechanics and Quantum Chemistry; Nuclear Structure;
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Nuclear Chemisty; Nuclear Reactions and Nuclear Energy; Radiation Chemistry;
Nucleosynthesis of Elements; Chemical Periodicity of the Elements.
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Volume 2
Bonding Theories (VBT and MOT) of Covalency; Strucutre and Reactivity of
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Covalent Compounds; Stereochemical Nonrigidity and Fluxionality; Molecular
Symmetry and Point Group; Solid State Chemistry - Structure and Bonding;
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Magnettc--and Ferroelectric Materials.
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Volume 3
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Bonding in Metals and Metal Clusters; PSPT - Wade's Rule and Jemmi's Rule;
Electric Conductivities of Solids; Semiconductors and Superconductors; Hydrogen
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Bonding and other Weak Chemical Forces; Supramolecular Systems and
Molecular Recognitions; Acids and Bases and Ionic Equilbria; Nonaqueous
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Solvents and Ionic Liquids; Redox Potentials, Formal Potentials and Applications;
EMF Diagrams; Electroanalytical Techniques; Photoredox Reactions; Oscillating
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Reactions
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Volume 4
Complex Compounds - Introduction; Structure; Stereochemistry and Isomerism;
Nomenclature, Bonding Theories (VBT, CFT, LFT and MOT); Applications of CFT;
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J.T. Distortion; Spectrochemical Series; Stabilities of Complexes.

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Volume 5
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Metal··€omplexes - Reaction Mechanisms (Ligand Substitution, Isomerisation,

Racemisation, Electron Transfer and Photochemical Reactions); Electronic
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Spectra.
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Volume 6
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Magnetochemistry and Magnetic Properties of Metal Complexes; Struct.ure,

Bonding and Reactivities of Organometallics including Metal Carbonyls and
Nitrosyls; Organometallics as Catalysts.
Volume 7
Application of Metal Complexes in Analytical Chemistry and other Fields; Theory
and Applications of Spectroscopic Methods (IR, Raman, NMR, ESR, Mossbauer,
NQR, Mass Spectrometry, UV-VIS, UV-PES)
Fundamental Concepts of
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Asim K. Dos
MSc (Gold Medalist CU), PhD (CU), DSc (Visva Bharati)
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Professor of Chemistry
Visva Bharati University, Santiniketan 731235
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West Bengal (India)

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Mahua Des
MSc (CU), PhD (Visva Bharati)
Former Research Associate, Department of Chemistry
Visva Bharati University, Santiniketan 731235
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West Bengal (India)

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A tribute to
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to the cyclonic monk Swami Vivekananda (186.3-1902)
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on the occasion of his 150th birth anniversary
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This Page is Intentionally Left Blank

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r"f'te present volum~s 4-7 are in continuation of the existing title Fundamental Concepts
.1. of Inorganic Chemistry. The classnotes and valuable suggestions received from the
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esteemed readers have been shaped in these volumes.
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These volumes cover the structure and bonding (VBT, CFf, and MOT), stability and
reactivity, spectral and magnetic properties ofmetal complexes in depth. Kinetics and reaction
mechanisms of ligand substitution, electron transfer and photochemical reactions have been
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included. Magnetochemistry and organometallic chemistry have been covered. Applications

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of different spectroscopic techniques (Raman, IR, NMR, ESR, Mossbauer, UV-VIS, UV-
PES, etc.) have been discussed to widen the utility of the series. In developing the present
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extension, we have taken all the measures to retain the basic features of the existing title.
In preparing the manuscript, we have freely consulted the books and reviews of the earlier
authors and have borrowed their ideas whenever it has been required. These sources are
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listed and acknowledged at the end of the text. We are grateful and indebted to these authors.
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In reality, we have picked up flowers from these gardens to prepare the garland to worship
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the goddess of learning.

We are extremely thankful and grateful to Mr SK Jain, Managing Director, CBS Publishers
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& Distributors, for his continued support. We are thankful to Mr YN Arjuna, Senior pirector,
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Publishing, Editorial and Publicity, and the DTP staff for taking the trouble in pEocessing
the manuscript.
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In spite of our best efforts, some mistakes and misconceptions might have crept in for
which we beg to be excused. Constructive criticism and suggestions are always welcome to
better the presentation.
Asim K. Das
Mahua Das
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Preface vii
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8.1 Elements of Magnetic Properties and Terminology 1087
8.2 Classification of Magnetic substance 1097
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8.3 Magnetically Dilute and Concentrated Substances: Cooperative Magnetism -
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Antiferromagnetism, Ferrimagnetism and Ferromagnetism 1097
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8.4 Ferromagnetism and the Related Phenomena Like Magnetic Domains, Hystresis Loop:
Application of Hard and Soft Ferromagnetic Substances 1097
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8.5 Temperature Dependance of Magnet~c Susceptibility of Different Types of Magnetic
Materials: Curie's Law, Curie-Weiss Law and Langevein-Debye Equation 1097
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8.6 Pathways of Antiferromagnetic Interaction 1100
8.7 Detection of Ferromagnetism and Antiferromagnetism 1100
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8.8 Comparison of the Properties of Different Types of Magnetic Substances 1101

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8.9 Sources of Paramagnetism and Magnetic Properties of an Electron 1101

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8.10 Origin of Diamagnetism and Lorenz's Law 1103

8.11 Pascal's Constants and Diamagnetic Susceptibility 1106
8.12 Experimental Procedure for Determination of Magnetic Susceptibility by Gouy's
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Balance Method 1109

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8.13 Spin-Orbit Coupling Constanl~: Splitting of the Energy Levels: Lande Interval Rule 1116
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8.14 Paramagnetism and Thermal Energy 1120

8.15 Quenching of Orbital Contribution to Magnetic Moment by Crystal Field 1128
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8.16 Mixing of the Ground State with the Excited State via Spin-Orbit Coupling:
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Orbital Contribution from the Excited State through Spin-Orbit Coupling 1132
8.17 Mixing of the Excited Terms with the Ground State Term through the Second Order
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Zeeman Effect 1135

8.18 Magnetic Properties of the Complexes of First Transition Metal Ions 1139
General Magnetic Behaviour of the Complexes of 3D-Metal Ions ; Comparison of the
Magnetic Properties of Fe(II), Co(ll), Ni(II) and Cu(II) ':omplexes
x Fundamental Concepts of Inorganic Chemistry
8.19 Magnetic Properties of the Lanthanides and Actinides Magnetic Properties of the
Lanthanides ; Magnetic Properties of the Actinides 1148
8.20 Comparison of the Magnetic Properties of the A, E and T Terms: Temperature
Dependance of magnetic properties 1154
Magnetic Properties of the Complexes with the A and E Ground State Terms; Magnetic
Properties of the Complexes with the T-ground State; Magnetic Properties of the 1st Transition
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Metal Ion Complexes (with the T-ground state) at Different Temperatures
8.21 Magnetic Properties of the Complexes of Second and Third Transition Series 1166
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8.22 Characteristics of the Second Order Zeeman Effect Contributing to the Magnetic
Susceptibility 1167
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Characteristic Features of the 2nd Order Zeeman Effect Contributing to the Magnetic
Susceptibility; Some Representative Examples Having XM(TIP) or XM(2nd order)
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8.23 Consequence of Electron Delocalisation on Magnetic Properties: Evaluation of the
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Delocalisation Factor i.e. Orbital Reduction Factor 1173
8.24 Magnetic Properties for the Thermal Equilibrium Between the High Spin and Low Spin
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States in the Crossover Region 1175
Condition for Thermal Equilibrium between the High Spin State and Low Spin State of the
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Octahedral Complexes; Effect of Pressure on Spin-State Isomerism ; Anomalous Magnetic
Properties due to Spin-state Isomerism in the Octahedral Complexes; Thermally controlled
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Spin Transition Curves; Examples Illustrating the Magnetic Properties of Complexes Showing
the Spin-State Isomerism in the Octahedral Complexes; Spin-State Equilibrium in the Mixed
Ligand Tetragonal Complexes of Nickel(II); Spin-State Isomerism in the Square Planar
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Complexes; Spin-State Isomerism in the Five Coordinate Complexes

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8.25 Magnetic Properties of the Intermediate Spin and Spin Admixed States in the Five
Coordinate Square Pyramidal and Square Planar Complexes 1191
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Possible Spin States and Intermediate Spin State; Possible Spin States and Intermediate Spin
State in the Four Coordinate Square Planar Complexes; Spin-Admixed Ground State; Magnetic
Properties of the Square Pyramidal Complexes of Fe(III) in Terms of Intermediate Spin and
Spin-Admixed States; Magnetic Properties of the Square Pyramidal Complexes of Fe(II) in
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Terms of the Intermediate and Spin-Admixed States; Thermally Controlled Spin Equilibrium
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Involving an Intermediate Spin

8.26 Structural Isomerism Leading to the Spin-State Equilibrium 1196
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Octahedral - Square Planar Equilibria for the Nickel(II) Complexes; Monomer-Polymer

Equilibria among the Nickel(II) and Cobalt(II) Complexes; Square Planar-Tetrahedral
Equilibrium of the Ni(II) Complexes; Octahedral-Tetrahedral Equilibrium
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8.27 Anomalous Magnetic Moments of Some First Transition Metal Complexes 1205
8.28 Magnetic Exchange Interactions: Superexchange Interactions in Terms of Goodenough-
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Kanamori-Anderson Rules (GKA Rules) 1206

Superexchange Phenomenon; Statement of the GKA Rule; GKA Rules in Terms of Overlap
Integrals: Orthogonal and Nonorthogonal Orbitals; Orbitals Involved in 180° and 90°
Superexchange Interactions ; Magnetic Exchange Interaction (180°) in Some Representative
Compounds in Terms of the GKA Rules; Magnetic Exchange Interaction (90°) in Some
Representative Compounds in Terms of the GKA Rules; Ferromagnetism in the Copper(II),
Oxidovanadium(IV) and Oxidomolybdenum(V) Complexes
8.29 Interpretation of Magnetic Exchange and Goodenough-Kanamori-Anderson Rules
(GKA Rules) in Terms of the Multicentred Molecular Orbitals Formation 1225
Molecular Orbital Approach for the 180° Superexchange Interaction; Molecular Orbital
Approach for the 90° Superexchange Interaction
Contents xi
8.30 Antiferromagnetism in the Magnetically Concentrated Systems: Pathways of

Antiferromagnetic Interactions 1229
Types of Antiferromagnetic Interaction; Mechanism of Antiferromagnetic Interaction
8.31 Cooperative Magnetic Interaction in the Copper(II) Dinuclear Complexes 1230
Antiferromagnetic Interaction in Carboxylato-Bridged Dinuclear Copper(II) Complexes:
Dimeric Copp"er(II) Accetate Monohydrate; Cooperative Magnetism in the Di-
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Hydroxidobridged Dinuclear Copper(II) Complexes in Terms of the Structural Parameters;
Antiferromagnetic Interaction in the Other Dinuclear Copper(II) Complexes
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8.32 Antiferromagnetic Coupling in Other Metal Complexes 1245
Magnetic properties of the Dimers of Oxidovanadium(IV) and Oxidomolybdenum(V)
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Complexes; Dinuclear Complexes of Titatinum(III); Single Oxido-bridged vs. Hydroxido-
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bridged Dinuclear Complexes of Chromium(III) (cf Sec. 8.28.5a for 1800 superexchanges in
d 3 systems); Strong Antiferromagnetic Interaction in Dimeric Chromium(II) Acetate
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Monohydrate; Diamagnetic Character of [Mn2(CO)1O]; Other Examples of Metal-Metal
Bonding Leading to an Antiferromagnetic Coupling; Diamagnetism in [M 20X lO]4- (X = Cl,
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Br; M = Ru or Os); Antiferromagnetic Interaction in KMF3 and K 2MF4 (M = bivalent transition
metals) and Transition Metal oxides; Antiferromagnetic Interaction in Some
Metallobiomolecules
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8.33 Some Special Cases of Cooperative Magnetism: Ferrimagnetism, Canting and Weak
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Ferromagnetism 1256
Ferrimagnetism ; Canting and Weak Ferromagnetism
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8.34 Competing Interactions and Spin Frustation 1258

" Antiferromagnetically Interacting Spins in a Triangular Arrangement; Antiferromagnetically
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Interacting Spins in a Tetrahedral Arrangement: A Spin Frusted System ; Examples

Experiencing Competing Interactions
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Exercise 8 1262
Appendix-VIII: Derivations of Some Important Relations (Including Van-Vleck Equation
and Bleaney-Bowers Equation) of Magnetochemistry 1278
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...nrJMetal Carbonyls: n-Acid Metal Complexes:

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~'f7"~_~,!7t~iEl:I\1(t:lxl~",(ting·Characteristics 1295-1501
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9.1 Introduction and Important Milestones of Historical Importance 1295

Definition and criteria of Organometallic Compounds; Characteristics of the Metal-Carbon
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(M-C) Bonds; Important Milestones in the Development of Organometallics

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9.2 Types of Organometallic Compounds on the Basis of the Nature of Metal-Carbon Bond 1298
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9.3 Effective Atomic Number Rule: Eighteen Electron (18e) Rule: Sixteen Electron (16e) Rule 1299
9.4 Metal Carbonyls 1299
Introduction; Different Types of CarbonyIs and Their Properties; Application of the 18-Electron
(18e) Rule to Metal Carbonyls ; Characteristic Features of the Bridging and Terminal CO
Groups: Factors Favouring the Nonbridged or CO Bridged Structures; Fluxionality (i.e.
Stereochemical Nonrigidity) in Carbonyls; Coordinating Behaviours of the CO Groups in
Carbonyls; Preparation of Metal Carbonyls, Carbonyl Halides, Carbonyl Hydrides and
Carbonylates; Reactivities and Mechanistic Aspects of Metal Carbonyls and Carbonylates;
Bonding in Carbonyls with Special Reference to the Linear M-C-O Groups and Jl2-CO
group; Evidences in Favourof1t-Back Bonding, Le. Retrobonding in Metal Carbonyls; Infrared
Spectroscopy of Metal Carbonyls; Unusual C-O Stretching Frequency and Nonclassical
xii Fundamental Concepts of Inorganic Chemistry
Carbonyls; Effect of Pi-back Bonding and Magnitude of 10Dq in the Isoelectronic and
Isostructural Carbonyls ; Structural and Bonding Properties in Polynuclear Carbonyls; Bonding
and Structures of Polynuclear Carbonyls In Terms of Polyhedral Skeletal Electron Pair Theory
(PSPT); Physical and Chemical Properties of Carbonyls in General; Carbonylate Anions and
Carbonyl Hydrides: Synthesis, Structure and Properties; Carbonyl Halides: Synthesis, Structure
and Properties
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9.5 Other Important x-Acid Ligands and their General Behaviour 1354
9.6 Metal Nitrosyls: Metal Complexes with Nitric Oxide as Ligands 1357
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Coordinating Behaviour of NO ; Factors Favouring the Linear and Bent M-N-O Linkage;
Chemical Distinction between the Linear and Bent M-N-O Linkages; Comparison of the
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Linear M-C-O and M-N-O Bonds; Relative Instability of the Pure Nitrosyl Complexes:
Requirement of Electron Withdrawing Pi-acid Ligands to Stabilise the Nitrosyl Complexes;
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Difference in the Ligand Substitution Paths for the Carbonyls and Carbonyl-Nitrosyls;
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Synthesis of Nitrosyl Carbonyls and Other Mixed Ligand Complexes Containing the Nitrosyl
Ligands; Some Representative Nitrosyl Complexes of Importance
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9.7 Cyanido Complexes 1375
Characteristic Properties of CN- as a Ligand; Coordination Modes of CN-
9.8 Isocyanide or Isonitrile Complexes lc 1379
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9.9 Sulfur Dioxide (S02) as A x-Acid Ligand 1381
9.10 Phosphines and Phosphites as the x-Acid Ligands 1382
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9.11 Chemistry of Dinitrogen Complexes: Activation of Dinitrogen 1386

9.12 Chemistry of Dihydrogen Complexes: Activation of Dihydrogen 1390
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9.13 Chemistry of Dioxygen Complexes: Activation of Dioxygen 1391

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9.14 Different Types of Organometallic Compounds of the Main Group Elements and
Transition Metals 1400
9.15 Oraganometallics of the Main Group and Zinc Group Elements 1401
Synthesis of the Alkyl or Aryl Compounds; Structure and Properties of the Organometallics
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of Alkali Metals; Structure and Properties of the Organometallics of Group 2 (i. e. Alkaline Earth
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Group); Structure and Properties of the Organometallics of Group 13 Elements; Structures and
Properties of the Organometallics of Group 14 Elements; Organometallics of the Group 15
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Elements; Preparation and Properties of the Organometallics of Group 12 Elements

9.16 Sigma Bonded Organometallics of Transition Metals: Metal Alkyls, Aryls,
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Carbenes and Carbynes 1430

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Stability of the Sigma Bonded Alkyl and Aryl Compounds of the Transition Metals:
Thermodynamic Stability vs Kinetic Stability: Reactions of the Compounds; Conditions for
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Stabilising the Sigma-Bonded Organometallics; Synthesis of the Sigma-Bonded

Organometallics; Metal Carbene (i.e. Alkylidene) and Carbyne (i.e. Alkylidyne) Complexes
9.17 Alkene Complexes 1435
Introduction; Structure and Bonding in Zeise' s Salt and Stability of Complexes formed by
R2Cw CR 2; Complexes with Polyolefins-Both Conjugated and Isolated Double Bonds:
Complexes with the Chelating Dienes; Common Routes of Synthesis of Olefinic Complexes;
Reactivity of the Coordinated Alkenes; Fullerenes as Ligands and Fullerene Complexes
9.18 Alkyne Complexes 1447
Coordinating Behaviour of Alkynes; Common Routes of Synthesis of the Alkyne Metal
Complexes; Reactivity of the Coordinated Alkynes
Contents xiii
9.19 Allyl Complexes 1452

Coordinating Behaviour of the Allyl Group; Possible Stereoisomerism in the Allyl Complexes;
Fluxional Behaviour in the Allyl Complexes; Some Representative Examples of the Allyl
Complexes; Common Routes of Allyl Complex Synthesis
9.20 Complexes of Cyclic Polyenes: Carbocyclic Pi-Complexes 1459
Common Examples of Carbocycles with 1t-Electrons; Cyclobutadiene Complexes; Cyclo-
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pentadienyl Complexes; Arene Complexes: Benzene Complexes; Cycloheptatrienyl
Complexes: Cycloheptatriene and Tropylium Cation; Coodinating Behaviour of
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Cyclooctatetraene (cot)
Exercise 9 1488
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10.1 Important Types of Reactions of Organometallic Compounds 1502
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10.2 Ligand Substitution Reactions of the Carbonyl Complexes 1503
Effect of Electronic Structure on the CO Substitution Process; General Rate Law for the
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Nucleophilic Substitution of Metal Carbonyls; Dissociative Activation (D and Id) of
Substitution of CO Group; Associative Activation of Substitution of CO Group; Reactions of
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the Coordinated CO Ligand; Nucleophilic Substitution versus Cluster Fragmentation;
Photochemical Reactions of Metal CarbonyIs
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10.3 Properties and Reactivity of Fischer and Schrock Carbene Complexes 1512
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10.4 Metal Carbonyls as Nucleophiles and Bronsted Bases 1518

10.5 Insertion and Deinsertion Reaction 1520
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Characteristics of CO Insertion: Carbonylation and Decarbonylation Reactions; Olefin

Insertion and ~-Elimination; S02 Insertion into the Metal-Carbon Bond
10.6 Oxidative Addition or Oxad Reaction 1529·
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General Aspects of Oxidative Addition; Scope of the Oxidative Addition Reaction;

Stereochemistry of Oxidative Addition; Mechanism of the Oxidative Addition Reaction
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10.7 Reductive Elimination 1543

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10.8 Activation of C-H Bonds Through the Oxidative Addition 1545

Characteristic Requirements of the C-H Bond Activation; Examples of the C-H Bond
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Activation
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10.9 C-H Bond Activation through THE Sigma-Bond Metathesis 1549

10.10 Redistribution (i.e. Scrambling) Reactions 1550
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10.11 Pathways Leading to the Stereochemical Nonrigidity and Fluxional Isomerism in the
Organometallic Compounds 1552
Characteristic Features of the Stereochemically Nonrigid and Fluxional Molecules;
Stereochemical Nonrigidity in the Compounds of Main Group Elements and Classical
Coordination Complexes; Fluxional Behaviour in Organometallic Compounds
10.12 Reactivity of the Coordinated Ligands 1570
Principles behind the Activation of Coordinated Ligands: Factors Favouring the Nucleophilic
and Electrophilic Attack on the Coordinated Ligands; Activation of the Coordinated Ligands
and Function of Metalloenzymes; Activation of the Coordinated Ligands and Catalysis;
xiv Fundamental Concepts of Inorganic Chemistry
Activation of Dihydrogen (H 2) and 'C-H' Bond through Metal Ligand Interaction; Activation
of the Coordinated Ligand and Template Synthesis of Macrocyclic Ligands; Some
Representative Examples of Reactions at the Coordinated Ligands; Reactivity of the
CyclopentadienyI Rings of Ferrocene; Reactions of the Coordinated Ligands in Organometallic
Compounds; Characteristics of the Dioxygen Complexes, i. e. O2 as a Ligand: Reactivity of
Coordinated Dioxygen: Activation of O2 ; Characteristics of the Dinitrogen Complexes, i.e.
N2 as a Ligand: Reactivity of the Coordinated Dinitrogen: Activation of N2 ; Characteristics
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of the Dihydrogen Complexes, i.e. H 2 as a Ligand: Reactivity of the Coordinated H 2: Activation
ofH 2
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10.13 Catalysis by Transition Metal Complexes 1604
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Introduction and General Principles of Catalysis; Basic Reactions Involved in the catalysis
by Organometallic Compounds; Hydrogenation of Olefins by Wilkinson's Catalyst; Synthesis
yl
of Optically Active Compound in Enantioselective Reactions by Using Wilkinson's Type
m
Catalyst; Hydroformylation Reaction (Oxo-Process); Monsanto Acetic Acid Synthesis; Wacker
Process (Smidt Reaction): Paladium Catalysid Oxidation of Olefin; Olefin Metathesis
he
Catalysed by Schrock Type Carbene (i.e. Alkylidene) Complexes and Alkyne Metathesis
Catalysed by Metal Carbyne Complexes; Ziegler Catalyst and Ziegler-Natta Catatyst:
Polymerisation of Olefins; Metal Catalysed Cyclooligomerisation of Acetylenes; Catalysis
lc
in Preparation of Synthesis Gas and Water Gas Shift Reaction (WGSR); Synthetic Gasoline
by Using ZSM-5 Catalyst (Mobil Process); Synthetic Gasoline by Fischer-Tropsch Process;
ea
Catalytic Deuteration of Benzene
10.14 Photochemical Reactions: Photocatalyst (Ti0 2) 1642

th
Exercise 10 1642
e/
Appendices A-1-A-9
t.m
Appendix I: Units and Conversion Factors A-I

Appendix II: Some Physical and Chemical Constants A-3
e
Appendix III: Wavelength and Colours A-4

er
Appendix IV: Names, Symbols, Atomic Numbers and Atomic Weights of the Elements A-5
Appendix V: Some Useful Mathematical Relationships A-6
H
Appendix VI: Books Consulted A-9

k
Subject Index 1-1-1-5

lic
C
11. Application of Complex Compounds 1659-1718
ry
ra
12. Spectroscopic Methods (IR, Raman, NMR, ESR, Mossbauer,
UV-VIS, UV-PES) and Other Physical Methods in Chemistry 1719-2111
ib
yl
13. The Theory of Errors and Statistical Treatment of
Analytical Data 2112-2192
m
he
lc
ea
th
e/
t.m
e
er
H
k
lic
C
ry
ra
ib
yl
m
he
lc
ea
th

e/
t.m
e
er
H
k
lic
C
Magnetochemistry: Magnetic
ry
Properties of Metal Complexes
ra
ib
8.1 ELEMENTS OF MAGNETIC PROPERTIES AND TERMINOLOGY
yl
(cf. Sec. 11.16.1, Vol. 2)
m
(a) Pole strength (m): The active force (repulsive for the same type poles; attractive for the opposite
types of pole) between the poles of m 1 and m2 strength separated by the distance r in air is given
he
by Coulomb's law:
F(indyne) = ml~2, (CGSsystem); F(innewton)=(~) x ml~2,
lc (SI system)
r 4n r
J.lo (permeability in air) = 41t x 10-7 henry/meter; unit of pole strength in SI system = ampere meter,
ea
i.e. Am.
The unit pole is defined (in CGS system) as the pole that repels or attracts another unit pole placed
th
in air (or vacuum) one cm apart by a force of one dyne (i.e. F = I dyne for r = I cm in air and
ml=m2= I).
e/
(Note: In SI system, for r = I meter (in air), ml = m2 = I,

t.m
7
J.loxmtm2 _ 4nx10- xIxl -10-7 )
F 2 - 2 - newton.
4nxr 4nxl
If a pole of strength m is placed at the centre of a sphere of radius 1 cm, then the 41tm lines of
e
forces will come out from the surface of the sphere where 41t cm 2 is the surface area of the sphere.
er
Thus the lines of forces per cm 2 at the surface of the sphere is:
41tm
H
--=m
4n
(b) Magnetic induction (B) and Gauss's law: When a substance is placed in a magnetic field of
k
strength (H) (i.e. H lines of forces per unit area), the total lines of forces (B) (passing out per unit
lic
area of the sample) is equal to the sum of Hand 41t times of the pole strength induced per unit
area. The pole strength induced per unit area is called the intensity of magnetisation (denoted by
C
M or l) i.e.
I = m = ml ,A = area, 1 = distance between the poles.

A Al
1087
1088 FUNDAMENTAL CONCEPTS OF INORGANIC CHEMISTRY
1 = Magnetic moment
i.e.,
volume
Thus we can write:
B = H + 41t1, (Gauss's law)
~ ) =1 + 41tXv (in CGS system)
ry
or, ; = 1+ 41t(
ra
(c) Permeability: BIH is defined as the magnetic permeability (J.l). Thus J.l gives the measure of
concentration of the lines of forces per unit area compared to that in the vacuum.
ib
CGS system: J.l = 1 + 41t(11H) = 1 + 41tXv = 1 + 41tX; (Xv very often simply denoted by X), i.e.
Xv or X = (J.l - 1)/41t.
yl
m
he
lc
ea
th
(a) Diamagnetism (b) Paramagnetism (c) Ferromagnetism

e/
Fig. 8.1.1 Different types of magnetic bodies in a magnetic field. (a) Diamagnetism - repelling the lines of force;
t.m
(b) Paramagnetism-attracting the lines of force; (c) Ferromagnetism-attracting strongly the lines of force.
Note: In vacuum, B (magnetic induction) expressed in tesla (T) or weber per square meter is related
with H (field strength) expressed in ampere per meter as follows:
e
In air, B = JloH, (in SI unit).

= permeability in vacuum = 41t x 10-7 henry per meter, i.e.
er
J.lo H m- 1 or T m A-I (SI system)

But for a substance other than air, B may be greater or less than JloH and is given by: B = J.lo(H + I).
It may be noted that in Gaussian system, J.lo = 1 and unit of H is oersted (Oe) having the same
H
dimension of gauss. Taking B = 1 gauss, i.e. 10-4 T, we have:

k
B 10-4 T
= 41txIO-
lic
1 A -I . IOe 1 Am- I
J..lo 41tx 10-7 TmA- 1 41txI0-3 m ; I.e. 3
C
B (Wbm-2 )
Permeability (J..l) = ==> Wb A- 1m- I = Hm- I , H = WbA- 1
H(Am- l )
Unit of B (magnetic induction) is tesla (T) or Wb m- 2 (i.e. weber per square meter); unit of H
(magnetic field strength) is A m- 1 (ampere per meter). It indicates that the unit of permeability is henry
per meter (i.e. H m- I ) where henry (H) = Wb A-I (weber per ampere).
If the field is applied to a substance, then Band H are related as:
B = f.lH, J.l = permeability of the substance through which the lines of forces pass. •
The ratio, WJ.lo is called the relative permeability and,..it is denoted bx. J.lr.
MAGNETOCHEMISTRV: MAGNETIC PROPERTIES OF METAL COMPLEXES 1089
In terms of flo, the total magnetic induction (B) in a substance is expressed, in general, as follows:
SI system: B = JloH + JloI = flo(H + J) = flo(l + Xv)H = JlH.
i.e. Jl = Jlo(l + Xv) or, Jlr = 1 + Xv or, Xv = Jlr - 1
Magnetic susceptibility: Intensity of magnetisatiop (J) of a substance is directly proportional to the
field and it is given by:
ry
locH or, I = XvH , where XV (SI) = 4nxv (Gaussian)
The proportionality constant Xv is called magnetic susceptibility' (i.e. volume susceptibility) and
ra
it is a dimensionless quantity.
ib
Gaussian System: ~ = 1 and B =H + 41tI, or, ; =1 + 41t (~ ) = 1 + 41tXv
yl
(~ ) = Ilo + lloX v
m
SI System: B = !!oH + W, or, ; = Ilo + Ilo
he
= Jlo + f.loX; (X v very often simply denoted by X)
Jlo = I (in Gaussian system), 4nXGaussian = XSI ; flo (permeability of vacuum) = 4n x 10-7 H m- I
lc
(d) Magnetic susceptibility: I/H is defined as the volume susceptibility (Xv) and it gives the measure
ea
to which the substance is susceptible or sensitive towards the external magnetic field.
The volume susceptibility is generally described as the magnetic susceptibility (commonly
denoted by X) and it has no unit.
th
(e) Gram susceptibility (Xg) and molar susceptibility (XM) are expressed as follows:
e/
Xg = k, p = density of the substance

p
t.m
XM (molar susceptibility) = XgM (M = molecular mass of the substance).

=( ; )xv = (Molar volume) x (magnetic susceptibility)
e
er
_
-Xv
Mkgmol- _
-Xv -
I
(M) m 3
mo
I-I
pkgm- 3
H
(HI) = -VMH X _
NAil NAf.l
k
_m_ = - - - , where Jlm = magnetic moment per molecule

m
It leads to: XM = VM -
V H
lic
VM = molar volume; I = magnetic moment per unit volume.

C
molar magnetic moment N Jl

i.e. 1= = ~ where Jlm = magnetIc. moment per molecule
molar volume VM
(f) Units: Weber (Wb) is the unit of magnetic flux. The old unit 'maxwell' (= gauss x cm 2) equals to
10-8 Wb
Wb = kg m 2 S-2 A-I = V s, V = m2 kg S-3 A-I =N m A-I, A = ampere,
Wb m- 2 is the unit of magnetic induction (B) (i.e. magnetic flux density). Wb m- 2 is called tesla
(T), i.e., T = Wb m- 2 = kg S-2 A-I = N m- I A-I = kg S-2 A-I = V s m-2 = N C- I m- I s; C = A s
Unit of magnetic field strength (H) is given by:
. 0f B
unIt NC- 1 m - 1 s C -1 -1 A -1
-----= S m = m
unit of flo N C- 2 s2
Unit of Jl (= BIH) is obtained as follows:
B Wbm~ Wb
- 1 = Hm- 1 = kgms- 2A -2, H (Henry) = - .
ry
H Am- A
(Wb m- 2 = kg m 2 S-2 A-I m- 2 = N A-I m- 1, H = Wb A-I)
ra
XM is expressed in m 3 mol- 1
ib
Quantity Units (81) Other units
yl
Pole strength Am
Magnetic moment Am 2 =JT- I
m
Magnetic flux Wb = kg m 1 S-1 A-I =V s maxwell (= gauss x cm 2)
=NmA- I =Tm 2 = 10-8 Wb
he
B (Magnetic induction) Wb m- 2 gauss (G)
(weber per G = dyn esu- I
square metre)
or
lc = (g cm S-2) (g1l2 cm 3/2 S-I)
=gl/2 cm- l12 S-I
ea
T (tesla) = N C- I m- I s = kg S-2 A-I
H (Magnetic Am-I = C S-I m- I Oersted (Oe) (same dimension
th
field strength) (ampere per meter) as gauss)

Jl (Magnetic H m- I = N C- 2 S2 = Wb m-IA- I
e/
permeability) (henry per meter)

XM (Molar susceptibility) m 3 mol-I
t.m
Jlo (permeability in free space) = 4n x 10-7 H m- 1 (SI) = 1 (in Gaussian system)

Gaussian system: B = H where unit of H is oersted;
SI system: B = JloH where unit of H is A m- 1
e
(g) Conversion factors:

er
• 1 G (gauss) = 10-4 T (tesla) = 10-4 Wb m- 2

H
B 10-4 T
• 1 Oersted = - = 7 1 1 A m- 1 = 79.6 Am- 1
3
flo 41t X 10- T m A- 41t x 10-
k
= 4nXM(Gaussian) x 10-6,
XM(SI)
lic
e.g. XM =8 X 10-3 cm 3 mol- 1 (say) then XM(SI) = 41t(8 10-3 X 10-6 ) m 3 mol- 1
X
= 41t x 8 X 10-9 m 3 mol- I

C
XM in mol- 1 m 3 (SI), XM in mol- I em 3 (in Gaussian system).
. 1 I M
• 41tXGaussian = XSI where Xv or SImp y X = -
H
Of - ,
H
a unitless quantity.
Illustration 1: If Xv= 599; Jl = ? Jl = Jlo(1 + Xv) = 4n x 10-7 (1 + 599) = 241t x 10-5 Wb Am-I.
Illustration 2: H = 7.5 Oe; iron rod of 23 em x 1.2 em x 0.5 em; Jl = 640 (CGS unit).
Find the value of magnetic moment.
fl = 1 + 41t(1 IH); Of, 640 = 1 + 41t1/7.5; or, 1= 639x7.5/(41t) (CGS unit)
I = magnetic moment/volume = magnetic moment/(23 x 1.2 x 0.5)

i.e. magnetic moment = 639 x 7.5 x 23 x 1.2 x 0.5/(41t) = 526.5 (CGS unit)
(h) Magnetic moment: The basic unit is called Bohr magneton (flB)
_ eh ( .) (4.8xl0- 10 esu) x (6.626 x 10-27 ergs)

flB or M B - - - - , CGS unIt = .
41tm e c 4 x 3.14 x 9.1 x 10-28 g x 2.99 X 10 10 cm S-l
ry
= 9.274 X 10-21 esu erg g-1 cm- 1 S2 = 9.274 X 10-21 erg G- 1
ra
[esu = g1/2 cm 3/2 S-I, G = g1l2 cm- 1I2 S-I]
SI unit of magnetic moment which is the product of pole strength and magnetic length =A m x
ib
m =A m 2 = J l 1
yl
eh (1.602 x 10- 19 C) x (6.626 X 10-34 J s)
m
11 B or M B = 41tm ' (SI unit) = 4 x 3.14 x 9.1 x 10-31 kg
e
10-24 C J S kg- 1
= 9.274 X
he
10-24 J T- 1 (T = kg S-1 C- 1)
= 9.274 X
(i) 1M: From definition, we can write: lc
ea
XM = XgM = (X; )M = Xv (;) = XVVM; VM = molar volume
th
i.e. XM = XVVM = (~ }VM = (:~) (~ ) = N~fi, (c/. I = magnetic moment/volume)

e/
t.m
2 - 2 2
fl H NAfl N A flm H
jI = _m- , (see Appendix VIII D); i.e. XM =- - = - x - - =NAflm
--
3k B T H H 3k B T 3k B T
iI =component of flm along the direction of the field) depends on temperature. Detailed calculation
e
shows that when a paramagnetic substance having the flm magnetic moment is placed in an
er
external field, the paramagnetic molecules (acting as the tiny magnets) will try to orient parallel
to the field direction. But, thermal orientation will try to oppose the parallel orientation of the
H
molecules. This orientation effect (ZM) on XM was calculated by Langevin from the statistical
consideration as given below:
k
1 fl2 N
lic
ZM DC - or, ZM = piT where the constantp = ~ (cj.Appendix-VIIID)

T 3k B
C
i.e. ZM = NA fl;;/3kB T
Here it should be mentioned that the applied field also induces a magnetic moment that is deter-
mined by magnetisability (a). Thus the total molar magnetic susceptibility (XM) is given by:
XM =NAa+ZM =N A (a+fl~/3kBT)~NA (fl~/3kBT),(CGS system)

i.e. in general, XM = A + BIT (cf. Curie-Langevin-Debye equation).
In terms of SI-system, it is: XM = N A (a + flofl;n 13kBT ) ~ N Aflo (fl~ 13kBT ), (SI system)
The contribution of a is negligible.
XM (Molar susceptibility) = NA ( ~~
3k B T
), (CGS or Gaussian system)
XM = NA (~o~~], (SI system)
ry
3k T
B
J.lm = magnetic moment of a single molecule of the substance,
ra
J.lo = permeability in space (i.e. vacuum) = 4n x 10-7 H m- I
J.lo = 4n x 10-7 Wb A-I m- I = 4n x 10-7 N C-2 S2
ib
or,
kB = Boltzmann constant, T = temperature in Kelvin scale.
yl
Note: The readers are suggested to follow the meanings of the symbols: J.l (permeability of a
m
substance); MD(permeability of air or free space); Jl r == Jl/~o ; J.lm = magnetic moment per molecule;
he
~ (component of J.lm along the direction of field); IlB (Bohr magneton); Xg (gram susceptibility);
XM (molar susceptibility) = MX g ; Xv(simply X) denoting volume susceptibility or simply magnetic
susceptibility. lc
ea
~
kTX ..
(j) XM and J..I.m: Jl m == B M, (In GaussIan system)
NA
th
3xl.38xl0- 16 erg K- 1 xTKxXMcm3mol-1

e/
6.023 x 10 23 mol- 1
t.m
= ~6.87 x lO--4° XMT erg em 3 = 2.63 x 10-20 JXMT erg 0-

1
[erg = g cm 2 S-2, G = gi/2 cm- I12 S-I, i.e. erg cm 3 = erg 2 G- 2]

e
J.lm is generally expressed in B.M., i.e. J.lB

er
1 B.M. = 9.27 x 10-21 erg G- I

It leads to:
H
2.63 x 10-20 --
~m ==-~(JXMT)B.M.=2.83JXM T B.M.
k
9.27 x 10
lic
J.lm may be calculated directly as follows:

C
3 x 1.38 X 10- 16 erg K- 1 x TK X XM cm 3 mol- l

6.023 x 10 23 mo!-1 x(9.27 x 10-21 erg 0- 1 )2
== 2.83 JXMT B.M.

(k) XM and Jlspin: If the resultant magnetic moment (J.lm) is believed to be due to the spins of the
unpaired electrons only, then J.lm is given by:
II-
r-vm
== II . .
t""spm"
== 2 '5(5 + 1) t""
liB; 5 ==!!.- where n = number of unpaired electrons.
2
XM =N A ( fl~
3k BT
), (in Gaussian system)
=~(2JS(S+I)f.lB/ = 4f.l~NA S(S+I)

3k BT 3k BT
ry
4x(9.274xlO-2I erg a- I )2 x (6.023 x 1023 mol- l )
ra
( )
= 16 1
S S+1
3x(I.38xI0- erg K- )x298 K
ib
= (1.68 X 10-3 erg G-2 mol-I) x S(S + 1)
yl
= 1.68 X 10-3 x S(S + 1) erg G-2 mol-I, (at 25°C)
m
= 1.68 x 10-3 x S(S + 1) em 3 mol- 1
= gl/2 em- l12 S-I, erg = dyn em, dyn = g cm S-2]
he
[G
2
Aflmflo (. SI )
(1) XM and J.1m: XM = N 3k T ,In system lc
B
ea
or, fl m =
th
e/
t.m
7396.94xl0-24 ~ ~
= 24 \jXM T B.M. =797.6\jXM T B.M.
9.274 x 10-
e
(cf 1 B.M. = 9.274 x 10-24 J I I )

er
Thus ~m can be directly calculated as follows:

H
k
lic
3 x 1.38 X 10-23 JK- 1 T K x XM m3 mol- 1

C
6.023 x 10 23 mol-I x 41t x 1O-7 N C-2 S2 x (9.274 X 10-24 JT- 1 )2
= 797.6)XMT B.M., (flB = 9.274 X 10-24 J T- 1) .
(m) XM: XM = ;k T
N fl2Jl
B
m 0 , (SI system)
Taking Jl m = J.!spin-only (simply Jlspin) = 2)S(S + 1) Jl B' we can write:

(6.023 X 10 23 mol-I) X 4 X (9.274 X 10-24 J r 1)2 x41t X 10-7 Ne 2 s2 X S(S + 1)

3x1.38x10-23 JK- I x298 K
ry
= 4n(1.68 x 10-9) X S(S + 1) J T-2 N C-2 S2 mol- l = 4n(1.68 X IO-9)S(S + 1) m 3 mol- l
ra
[T = kg S-l C- 1; J = N m; N = kg m S-2]
ib
Calculation of XM (Molar magnetic susceptibility) at 298 K (i.e. 25°C) from the Jlspin-only values.
= 41tX M(Gaussian) X 10-; XM(sI)

6· 1-1 3 . I-I 3
yl
XM(sI) In mo m ;XM(Gaussian) In mo cm.
m
Table 8.1.1 Spin-only magnetic moments and molar magnetic susceptibility (XM)
he
No.o/unpaired S=!!.. J.1s p in-only (H.M.) 1M
electrons (n) 2
= 2~S(S + 1) f-lB
lc Gaussian system SI system
=~n(n+2)f-lB (em 3 mort) (m 3 mort)
ea
1/2 1.732 1.26 x 10-3 15.82 X 10-9
th
2 2/2 2.828 3.35 x 10-3 42.07 X 10-9

e/
3 3/2 3.873 6.29 x 10-3 79.0 X 10-9

4 4.899 10.08 x 10-3 126.61 10-9
t.m
4/2 X
5 5/2 5.916 14.67 x 10-3 184.25 X 10-9
= MX Xg = M( ~ ) =( ;
e
• XM )Xv = (Molar volume) X (magnetic susceptibility) = VM X Xv

er
~ l
H
Xv ( = a unitless quantity i.e. unit of molar volume is the unit of XM'

k
Xv: unitless, 4nXV(Gaussian) = XV(SI)

lic
3 1 3 I
XM(sI) =41tX M(Gaussian) X 10-6; XM in cm mol- (Gaussian), XM inm mol- (SI).
C
(n) Illustration to calculate J..LetT or Ilspin from the XM values at 293 K.

(NH4)2CO(S04)2·6H20 shows X~orr = 1.11 X 10-2 cm 3 mol-I, (in CGS system)
corr
3k TX
Jl tf
e
= B
N
M = 2.83~X':;rrT B.M. = 2.83Jl.ll X 10-2 X 293 B.M.; T = 293 K
A
= 5.10 B.M.
In SI system, xttorr = 4n x 10-6 X 1.11 X 10-2
= 13.94 X 10-8 m3 mol- I
3kBTX~rr ~ "
rr X293 B.M.
II .Ir
t"'eJJ
= N = 797.6 XCMo
Af.lO
=797.6~13.94X10-8 x 293 B.M. = 5.10 B.M.
ry
Alternatively, f.leff can be calculated as follows:
ra
3 x 1.38 X10-23 J K- 1 x 293 K x 13.94 x 10-8 mol- 1 m 3
f.leff = 6.02 x 10 23 mol- 1 x4x3.14xl0-7 N C- 2 S 2
ib
yl
= 4.75 X10-23 JT- 1 = 5.10 B.M.
m
Problem 1: A substance (molar mass = 0.395 kg mol-I) possesses density 1.92 x 103 kg m-3 and X (at
293 K) =6.7 X 10-4. The diamagnetic correction is =2.5 X 10-9 mol- I m3 • Find XM' Ileff and number of
he
unpaired electrons assuming Ileff = Ilspin-only.
Solution: (a) In terms of SI units:
lc
=X( ; ) =X x (molar volume) = XVM;
ea
XM (X stands for Xv )
th
1
6.7 X10-4 x 0.395 kg mol-
----------.,;;~-- =.1 38 x 10-7 mo1-1 m 3
1.92 x 10 3 kg m-3
e/
X~rr = 1.38 X10-7 - (-2.5 X10-9 ) = (1.38 + 0.025) x 10-7mol- 1 m 3

t.m
e
J.leff = 797.6~X~rrT B.M.

er
= 797.6~1.405 X10-7 x 293 B.M.

H
= 5.10 B.M."
k
=J.lspin-only =2~S(S + 1) B.M. =2~%(% + 1) B.M.

lic
J.leff
C
=~n{n + 2) B.M. = 5.10 B.M.

It leads to n= 4 (taking the nearest integer):
(b) In terms of cas system:
6.7 x 10-4
41tX(CGS) = X(SI); or, X(CGS) = 41t
M = 395 g mol-I, p = 1.92 g cm-3

XM
_ (M)_- 6.7xI0-4 x--mo
-X -
395 I-I
cm
3
P . 41t 1.92
= 1.09 x 10-2 mol- I cm 3
If may be noted:
ry
41tX M (CGs) x 10-6 = XM(sI)
ra
i.e. 41t x 1.09 X 10-2 x 10-6 = 13.7 X 10-8
7 I 3
or, = 1.37 x 10- mol- m
ib
XM(sI) .
9
2.5 X 10- _ -0 0199 10-2 I-I
yl
dia _ 3
XM(CGS) - -6 - . x mo cm
41t x 10
m
X~rr = (1.09 + 0.0199) 10-2 mol- I cm 3 = 1.1099 x 10-2 mol- I cm 3
he
!leff = 2.83Jxc;;rrT B.M. = 2.83J1.1099 x 10-2 X 293 B.M. = 5.10 B.M.
lc
Problem 2: A complex of molecular mass 250 possesses two unpaired electrons per molecule. Calcu-
late X (Given: p = 4 g cm- 3). (T = 298 K)
ea
Solution: Number of molecules per unit volume (i. e. 1 m3) that contains plM moles of the substance
is given by:
th
NAP (6.023 x 10 23 molecules mol- 1 )(4,000 kg m -3) 27 -3

e/
n=--= I =9.64xl0 moleculesm

M 0.250 kg mol-
t.m
l
Here, S=2x-=1
2
e
n x 4S (S + 1) x fl ~ x flo
er
X= 3k T
B
H
(9.64 X 10 27 molecules m -3) x 4 xl (1 + 1) x (9.274 x 10-24 J r 1

)2 x 4 x 3.14 X 10-7 N C-2 S2
3xl.38xl0-23 JK- 1 x298 K
k
lic
= 1.14 x 10-3 (dimensionless quantity).

C
· - ~ I - magnetic moment
cf . X I.e. Xv - , - ,
H volume
I = molar magnetic moment = N AiIav

molar volume VM
2
(n) 4S (S + 1) fl ~flo jIav = !l H , see Appendix vmD
3k B T .
3k BT
8.2 CLASSIFICATION OF MAGNETIC SUBSTANCE (cf. Sec. 11.16.2, Vol. 2)

Depending on the relative values of Jl ( = BIH) and on the nature of sign of magnetic susceptibility
Xv or simply X (= IIH), the magnetically diluted substances can be classified as:
diamagnetic and paramagnetic substances.
fl = .Ii = I + 41tXv (Gaussian or CGS system)
ry
We have:
H
ra
Xv = 0 in vacuum or air, i.e. Jl = 1 or B = H. The substances having Jl) 1 are called the paramagnetic
substances while the substances having Jl ( 1 are called the diamagnetic substances. Thus, in the
ib
paramagnetic substances (B ) H), the lines of forces are more concentrated while in the diamagnetic
substances (B ( H), the lines of forces are decreased compared to those in air (ef Fig. 8.1.1).
yl
In terms of magnetic susceptibility (Xv = llH), for the paramagnetic substances, it is positive and its
value (CGS system) is in the order of + 10-4 while, for the diamagnetic substances, it is negative having
m
the value in the order of -10- 6 •
he
Paramagnetic substance: Jl ) 1, i.e. B ) H; it gives: f..lr ) 1, i.e. Jl ) JlD and Xv or simply X ) 0
Diamagnetic substance: Jl ( 1, i.e. B ( H; it gives: Jlr ( 1, i.e. Jl ( flo and Xv or simply X ( 0,
Xv z -10-6 (CGS)
lc
ea
8.3 MAGNETICALLY DILUTE AND CONCENTRATED SUBSTANCES:
th
COOPERATIVE MAGNETISM - ANTIFERROMAGNETISM,

FERRIMAGNETISM AND FERROMAGNETISM
e/
If the magnetic centres of a paramagnetic substance are widely apart and they do not mutually interact,
t.m
then such paramagnetic substances are called the magnetically dilute substances. But in the magneti-
cally concentrated substances, the individual magnetic centres can mutually interact. Depending on
the nature of interaction, cooperative magnetism may lead to: antiferromagnetism, ferromagnetism
and ferrimagnetism. Characteristic features of the cooperative magnetism have been discussed in Sec.
e
11.16.3 (Vol. 2).

er
8.4 FERROMAGNETISM AND RELATED PHENOMENA LIKE MAGNETIC DOMAINS,

H
HYSTERESIS LOOP: APPLICATION OF HARD AND SOFT FERROMAGNETIC

SUBSTANCES
k
These aspects have been discussed in Secs. 11.16.3, and 12.5.7-8 (Vol. 2).
lic
8.5 TEMPERATURE DEPENDANCE OF MAGNETIC SUSCEPTIBILITY OF DIFFERENT

C
TYPES OF MAGNETIC MATERIAL~: CURIE'S LAW, CURIE-WEISS LAW AND

LANGEVEIN-DEBYE EQUATION
These aspects have been discussed in detail in Sec. 11.16.5 (Vol. 2).
Here we shall discuss, in short, the origin of Curie and Curie-Weiss law. When an external magnetic
field (H) is applied on a paramagnetic substance, the paramagnetic molecules will try to orient in the
direction of the field. But, thermal excitation will try to orient the molecules randomly. Thus the effect
of Hand T (temperature) will mutually oppose and the molecules will orient in different angles
with the direction of the field. From the statistical consideration, Langevin showed that in this situation,
XM is expressed in terms of average effective contribution of magnetic moment (jI) per molecule.
NjI _ fl2 H .
XM = _A_ where fl = _m_, flm = actual magnetIc moment per molecule
H 3k BT
(see Appendix VIII D, at the end of this Chapter for its derivation)
N fl2 C
XM = ~ =-
ry
i. e. (Gaussian system),
3k BT T
ra
2
kB = Boltzmann constant, C = N Aflm (called Curie constant)
ib
3k B
and the above equation is call Curie equation (cf. Appendix VIII D).
yl
In terms of S.1. units, Curie equation is given by:
m
XM = N Aflofl~ ,.1.
(S unIt,
.)
he
3k B T
Temperature dependence of X is shown in Fig. 8.5.1. Curie equation indicates that XM is inversely
lc
proportional to temperature T (in Kelvin scale) and the plot I/XM vs. T should be a straight line passing
through the origin without any intercept. But, experimentally it has been found that in many cases,
ea
the straight line makes a finite intercept (8) on the temperature axis. For such systems, the equation can
be rewritten as:
th
C . 1 T 8
XM = T-8 I.e. - = - - - ; (cf. Fig. 8.5.1)
XM C C
e/
The above equation is called Curie-Weiss equation and 8 is called Weiss constant.
t.m
Q)
1 ,/ TIP
e
i
er
01--------
J, ~T(K)
~ '\ Diamagnetic
H
J...
~ Ferromagnetic
k
i Paramagnetic
lic
(above Tc and TN)

Neel--+ +- Curie point
point
C
I
I
I I
I I
I I
~I
8 8/'
~ Antiferromagnetic I
I /
I I /
1.1
I
I
I
(ii)
(i)
Fig. 8.5.1 Temperature dependence of magnetic susceptibility (X) of different types of magnetic substances; (i) magnetic
susceptibility - temperature (X vs. T) curves; (ii) l/X vs. T curves, (b) for Curie equation; (a) and (c) for Curie-Weiss
equation.
The origin of Weiss constant (8) is due to the mutual interaction among the individual paramag-
netic centres. In such cases, each magnetic centre is under the both internal and external magnetic
field.
The sign of e is quite important to characterise the nature of mutual interaction among the paramag-
netic centres leading to the cooperative magnetism.
(i) e =0 (paramagnetic bodies without any mutual interaction among the magnetic centres) (for the
ry
magnetically dilute substances).
ra
(ii) 8 = +ve (ferromagnetic interaction) } (for the magnetically concentrated substances)
(iii) 8 = -ve (antiferromagnetic interaction). cf. Fig. 8.5.1 (ii)
ib
It can be shown that,
yl
~ = 2.83~XM (T -8) B.M. (in COS units).
m
~=797.6~XM(T-8) B.M. (inSlunits).
he
Weiss constant (8), can be evaluated from the measurement of magnetic susceptibilities at different
temperatures.
lc
In the paramagnetic substances, random orientation of the molecules due to the thermal agitation
will reduce XM with the increase of temperature.
ea
In the ferromagnetic substances, below the Tc (Curie temperature), all the magnetic centres align
in the direction of the field causing a sharp increase in magnetic susceptibility. Above Tc, thermal
th
agitation is sufficiently high to break down the ferromagnetism and then they show the behaviour of the
normal paramagnetic substances, i.e. above Tc , Curie equation is obeyed.
e/
In the antiferromagnetic substances, below the Neel temperature (TN)' the magnetic centres align
in an antiparallel fashion to cancel out one another. Thus below TN' there is a sharp lowering of XM
t.m
values. Above TN' the thermal agitation is sufficiently high to prevent the antiferromagnetic interaction
and then the substance shows the behaviour of normal paramagnetic substances, i. e. above TN' Curie
equation is obeyed.
These are illustrated in Figs. 8.5.2.
e
er
I i III i 1/ I\ 1---.1 \ 1/ II I
H
(a)
k
lic
iiiiii i !i !i!
C
(b) (c) (d)
Canted antiferromagnetism Canted ferromagnetism
(e) (a-canting angle)
Fig. 8.5.2 Alignment of the individual magnetic dipoles in (a) paramagnetic, (b) ferromagnetic, (c) antiferromagnetic,
(d) ferrimagnetic and (e) canted magnetic substances.
Temperature Independent Paramagnetism (TIP): The second order Zeeman effect can generate
an induced paramagnetism that depends on the external field strength (H) but not on temperature. This
induced paramagnetism (called TIP) depends on the magnetisability of the substance. The Curie
paramagnetism (XM oc ~ ) is described as the first order Zeeman effect. The combined effect of 151
ry
order and 2 nd order Zeeman effect is expressed as follows:
2
ra
N Afl m C
XM =---+NAa=-+NAa
3k B T T
ib
The above equation is called Langevin-Debye equation. In the above equation, the 2nd term (i.e. 2 nd
order Zeeman effect) is relatively less important compared to the 1st term and this is why, in most of the
yl
cases, Curie equation is applicable.
m
Note: Diamagnetism vs. TIP: Magnetic susceptibilities of both diamagnetism and TIP are independent
of temperature but Xdiamagnetism is negative while XTIP is positive. However, both these x-values are quite
he
small.
8.6 PATHWAYS OF ANTIFERROMAGNETIC INTERACTION

lc
The metal-metal direct interaction and superexchange pathways leading to the antiferromagnetism
ea
have been discussed in Sec. 11.16.3 (Vol. 2). These are also discussed separately in Sec. 8.30.
8.7 DETECTION OF FERROMAGNETISM AND ANTIFERROMAGNETISM

th
Sometimes, many compounds may get contaminated with the ferromagnetic impurities from their pre-
e/
parative origins. Many Fe(III)-complexes are found to bear the ferromagnetic impurities, Fe(III)-
hydroxides. In such cases, if the susceptibility (XM) is measured at different field strengths, the
t.m
ferromagnetic susceptibility decreases towards a normal paramagnetic value at a very high field
strength. Actually, a plot of susceptibility vs. I/H is made and extrapolation to the infinite field is done
to obtain the limiting susceptibility. This variation of susceptibility with the field strength (H) is an
indication of the existence offerromagnetic impurity (cf paramagnetic XM does not depend on H).
e
Measurement of susceptibility at different field strengths does not give any strong indication of the
er
existence of antiferromagnetic interaction because it slightly depends on the field strength. To remove
the antiferromagnetic interaction, a magnetic dilution is necessary. This can be attained in two ways:
H
(i) by dissolving the substance in water or some suitable solvents.

(ii) isomorphous dilution in which the substance is placed in a diamagnetic host lattice which is
k
isomorphous with the substance under consideration.

lic
In the case of solution, we should be careful so that the coordination stereochemistry remains
unchanged.
C
For K 2[ReI6 ], the magnetic moment (J.lm) increases from 3.32 to 3.55 B.M. when the solid is dis-
solved in water. It indicates an antiferromagnetic interaction in solid K2 [ReI6 ]. If K 2[OsCI 6 ] is diluted
with the isomorphous diamagnetic substance K 2 [PtCI6], then the magnetic moment (J.lm) increases
from 1.44 B.M. to 1.94 B.M. It indicates the existence of an antiferromagnetic interaction in solid
K2 [OsCI 6 ]. In the case of isomorphous dilution, the dilution should be done at least by 10 times to
ensure the complete destruction of the antiferromagnetic exchange.
Both the techniques (i. e. dissolution and isomorphous dilution) will fail to detect the
antiferromagnetic interaction, if the antiferromagnetic interaction is of the intramolecular type (ef
detection of intra- and inter-molecular H-bonding through the dilution technique).
8.8 COMPARISON OFTHE PROPERTIES OF DIFFERENTTYPES OF MAGNETIC

SUBSTANCES
Type Origin Effect of Sign and magnitude Dependence Dependence

external field of %g (CGS unit) of%g on H of%g on T
Diamagnetic Orbital motion Weak repulsion Negative, sm'lJ.I Independent Independent
ry
(J!, J!r ( 1) (.... -1 X 10-6)
1
ra
Paramagnetic Spinning Moderate Positive, large Independent Xex:-
T
(J!, J!r) 1) and orbital attraction [.... + (10 - 100)
x 10~]
ib
motions of
the unpaired
yl
electrons
Ferromagnetic Parallel Very strong Positive, very *Dependent, **Dependent
m
(J!, J!r» 1) alignment attraction large
of spins of [- + (10 2 - 104)
he
the unpaired x 10-6]
electrons
Antiferro-
magnetic
Antiparallel
alignment of
Weak
attraction
lc
Positive, small
[.... +(0.1 -10)
May be
dependent
***Dependent
ea
(J!, J!r) 1) the spins of x 10~] (slightly)
the unpaired
electrons
th
* X decreases with the increase of H and a limiting value of X is obtained by extrapolation of the plot X vs. I/H; this
e/
limiting value (i.e. at infinite field) of Xrepresents the normal paramagnetic value (cf. Sec. 8.7). For the antiferromagnetic
substances, X slightly depends on H.
t.m
1
** Above To X ex: T but below Tc. X rises abruptly with the lowering of temperature.
1
*** Above TN' X ex: T but below TN' X decreases with the decrease of temperature.
e
er
8.9 SOURCES OF PARAMAGNETISM AND MAGNETIC PROPERTIES OF AN

H
ELECTRON (cf. Sec. 1.10.17, Vol. 1)

The origin of paramagnetism can be better explained by considering the classical picture of Bohr-
k
Sommerfeld atom. In this classical model, the negatively charged electron particles revolve in the
lic
specified orbits around the positively charged nucleus. The orbital motion of the revolving electron
produces a magnetic field perpendicular to the plane of the orbit. Similarly, the spinning motion of the
C
electron around its own axis produces a magnetic field. Thus, the orbital and spinning motions of the
electron are the sources of paramagnetism.
It has been shown in Sec. 1.10.17 (Vol. I), that the orbital magnetic moment (J.!/) is given by:
~/ =~l(z+l)~=~l(z+l)~, (CGS unit) i.e. ~/ =~l(I+l)~=g/~l(I+l)~, (g/ =1)

41tm e c
1 = azimuthal quantum number of the revolving electron, f3 (= eh/4nm ec, in CGS system) is the unit
of magnetic moment known as Bohr magneton (= 9.273 x 10-21 erg gauss-I).
The spin magnetic moment (l1s) is given by (cf Sec. 1.10.17, Vol. 1):
Il s =~4s(s+1)~=2)s(s+1)~=gsJs(s+1)~, gs =2,
gs commonly denoted by g and described as g-factor, s = spin quantum number of the revolving
electron.
We can write:
ry
Il, = -_e-Jl(l + 1) ~ =__e_ p ,; i.e., Il, oc p,.
2m e c 21t 2m e c
ra
where JlI =magnetic moment and PI =orbital momentum vector, the minus (-) sign indicates that JlI and
ib
PI act in the opposite directions.
It is evident that the orbital magnetic moment (JlI) is proportional to the orbital angular momentum
yl
I~;I
m
vector (PI) and the ratio, y/ = i.e. the ratio of the magnitudes of orbital magnetic moment and
he
orbital angular momentum vector is called the gyromagnetic ratio. It leads to:
lc
ea
4.8 X 10- 10 esu
th
2 x 9.1 X 10-28 g x 2.99 x 10 10 cm S-1

e/
t.m
Y, = _e_, (SI unit)

2m e
e
(1.6 X 1O-19c) = 8.8 X IOlD e kg-I

2 x 9.1 X 10-31 kg
er
YI can also be expressed as follows:

H
~ 9.27 x 10-21 erg G- 1 x2x3.14

Y,=--=
k
(h/21t) 6.62 x 10-27 erg s

lic
= 8.8 X 10 6 0- 1 S-I, (COS system)

C
For the spinning motion of the electron, similarly, we can write:
s
Ys(gyromagneticratio)= 1,ll =_e_, (CGS system)
,1
Ps mec
We can write: YslY, = 2.0 cf. f.l, = -P, (_e_J but f.l s = -P s
2m e c 2m e c
(~J' (see Vol. 1).
The Jls parameter can be written as (by taking gs or g = 2):
lIe ~ h ~ eh
CGS system: Il s = YsP s =- gysP s =- g x - x \ls(s + 1) x - = g~s(s + 1) x - -
2 2 mec 21t 41tm ec
=gJs(s + 1) B.M., (ignoring the sign)

g is called the g-factor, Ys is gyromagnetic ratio for the spinning motion of the electron. The value
ry
of g is 2.0 (see Sec. 8.15). Actually for the free electron, it has been found, g = 2.0023193 (experimental
values from esr-studies). In fact, Dirac's theory supports, g = 2.0.
ra
The additional part (= 0.0023 ... ) arises from the electromagnetic fluctuation in the vacuum surrounding
the electron. This can be rationalised by quantum electrodynamics.
ib
The g-value of an electron may differ from the free electron value depending on the nature of the
yl
orbital in which the electron resides.
Similarly, for the orbital motion, we can write:
m
~h ~ eh
CGS system: Il, = YIP, = gy,p, = g x -e- x "l\l + 1)- = g x vl(l + 1 ) - - ,
he
2m ec 21t 41tm ec
(ignoring the - sign)
Here, g = g, = 1. lc
ea
8.10 ORIGIN OF DIAMAGNETISM AND LORENZ'S LAW
(a) Oribital motion and diamagnetism: The phenomenon, diamagnetism exists only in presence of an
th
external magnetic field. The origin of diamagnetism can again be understood in the light of classical
atomic model, i. e. Bohr-Sommerfeld model. The orbital motion of an electron produces an electric
e/
current. When it is subjected to an external magnetic field, the interaction between the current and the
magnetic field (H) causes the orbit to precess (i.e. Larmor precession) around the direction of the
t.m
external field (H). In fact, normal of the orbit describes a cone about the direction of the field. This
precessional motion (angular motion = eH/2me c) is induced by the external field and direction of the
magnetic field generated due to the induced precessional motion is opposite to the direction of the
e
applied field. This opposing effect is described by the negative (-) sign.
er
H
H
,. --- ---... ........

I
/
"
------., \
k
\
' ........ r1 ,/
lic
C
Fig. 8.10.1 Precession of the electronic orbit in presence of an external magnetic field (H).
(b) Lorenz's law and diamagnetism: Thus the origin of diamagnetism can be understood by con-
sidering the moving electron in an orbit as the current flowing in a coil of wire. When such a coil
carrying the current is placed in an external magnetic field (H), according to Lorenz's law, the external
magnetic field (H) induces a current (due to the induced precessional motion of the orbit) to induce a
magnetic field to oppose the direction of the applied magnetic field. This leads to the diamagnetism.
In the case of a coil carrying the current, the induced magnetic field vanishes quickly due to the
ry
atomic resistance. Inside the atom, the electronic current does not experience any resistance and the
induced magnetic field exists so long as the external magnetic is present. It is also realised from the fact
ra
that the precessional velocity (=~) becomes zero when H becomes zero.
ib
2m e c
(c) Quantitative expression of the diamagnetic susceptibility (X<lia): The diamagnetic moment of
yl
an electron is given by:
m
he
e X(precessional angular velocity) x (precessional orbit radius )2
fl induced = fl ~ia = 2c
e x eH x '12 e 2 H ,?
lc
=- __1-2 ' (for a single electron)
ea
-----=--
2m e c x 2c 4m e c
th
2
Here, '1 is the mean square radius of the precessional orbit described by the orbit normal.
If the position of the electron in an orbit is defined by (x, y, z) assuming the nucleus to remain at the
e/
origin (0, 0, 0) then the orbit radius ('), for a time average, is given by:
t.m
,2 = x 2 + y2 + Z2 (cf the equation of a sphere and generation of a circle from the intersection of the
sphere).
The electron orbit can be oriented in the presence of a magnetic field in an infinite number of ways
e
.and all these orientations are equally probable. It leads to:

er
x2 = y2 = Z2 , i.e. mean values of the square of the coordinates along all the three axes are equal.
H
k
To determine, '1' we are to consider the xy-plane which is obtained by the projection of the orbit
lic
perpendicular to the direction of the field (assuming to be coincident with the z-axis). It gives:
C
r12 = x 2 + y2, (cf in general, '1

2
= x2 + y2 + Z2 ; in the present case, i.e. in the xy-plane, it gives
2
'1 =x 2 +y 2 ) .
i.e. 2
'1 = 2x 2 = 2 y 2 =-22"
r
3
, e2 H 2 2" _e 2 H -;- .
It gives: fldia = - - - - 2 X -r = - - - 2 r-, (for a SIngle electron)
4m e c 3 6m e c
2 2
, e Hr 2 . .
J.ldia =- - - 2 - ' r = mean square radIus of the orbIt.
6m ec
For a multielectronic system, we can write:
2H
ry
] -
/ldia =- [ 6~ec2 '2.,./
ra
For one gram atom:
ib
J.ldia (gram atom) =
yl
m
The molar diamagnetic susceptibility is given by:
(;J
he
XM(dia) = Xg x M= (Xv Ip)M = Xv
=(~ )VM • (VM =molar volume)

lc
ea
N x J.l .
= J.l dla. (gram atom) X -l:L;
V
th
I = magnetic moment/volume = A dla

VM H VM
e/
= J.ldia (gram at9m) = J.ldia X N A

t.m
H H
e
er
= -2.83 X 10 10 L1j2, (CGS system)

H
(d) Diamagnetism due to the spinning motion of electrons: The spinning motion of an electron in
presence of an external magnetic field will also produce the diamagnetism in the same way. But the
k
radius (- 10- 13 cm) of the spinning motion is too small compared to the radius of the orbital motion.
lic
From the given relation, it is evident that diamagnetic susceptibility is proportional L 1j2. Thus, it is
reasonable to conclude that the diamagnetism originated from the spinning motion of the electrons is
C
negligibly small compared to the diamagnetism developed from the orbital motion of the electrons.
(e) Diamagnetism from the spinning motion of the nucleus: It is known that Mia is inversely
1
proportional to the mass of the revolving charge, i.e. Xdia oc - . The mass of a spinning nucleus is much
m
higher than that of an electron. This is why, the diamagnetism produced from the spinning motion of
the nucleus is negligibly small compared to that produced from the orbital motion of an electron.
(I) Characteristics of the diamagnetic susceptibility: These are summarised here.
(i) It opposes the applied magnetic field. This is why, it is associated with a negative (-) sign.
(ii) Its magnitude is very small (-- -1 x 10-6 in CGS unit).

(iii) Diamagnetism produced by the orbital motion of the electron is only significant. The diamag-
netism originated from the spinning motions of the electrons and nucleus is negligibly
small.
(iv) Mia depends on the radius of the orbit. For the orbits of larger radius, Mia is relatively larger.
(v) Diamagnetism is developed in all types of substances whether the substance is containing the
ry
unpaired or paired electrons. But, if the substance is paramagnetic (i.e. presence of unpaired
ra
electrons), then the paramagnetic susceptibility (of larger magnitude) can overshadow the
diamagnetism (which is of much smaller value). Thus, diamagnetism is only noticeable when
ib
the substance contains only the paired electrons.
(vi) Xdia is an induced effect of the external magnetic field. Thus, it exists so long as the external
yl
field (H) remains present. It is known that the induced precessional velocity of the orbit is
responsible for the diamagnetism and this precessional velocity (= eH/2m e c) becomes zero when
m
the field becomes zero (i. e. H = 0)
he
(vii) The magnitude of ~dia depends on H but the magnitude of Mia does not dep~d on H. These are
evident from the mathematical expression of ~dia and Xdia.
(viii) Orbital motion of an electron does not depend on the thermal energy. This is why, diamagnet-
lc
ism is independent of the temperature.
ea
(ix) XM(dia) does not depend on the physical state of the substance because orbital motion of the
electrons does not depend on the physical state (i.e. gaseous, solid or liquid state).
th
8.11 PASCAL'S CONSTANTS AND DIAMAGNETIC SUSCEPTIBILITY

e/
From the mathemati<;al expression of Xdia, it is evident that to calculate Xdia. it requires the knowledge
of I1j2 which is uncertain. From the experimental findings, P. Pascal observed that the diamagnetic
t.m
susceptibility follows the law of additivity along with the constitutive corrections. In other words, the
diamagnetic susceptibility of a substance can be obtained by adding the contributions of the constituent
atoms and bonds. This is expressed as follows:
e
= Lll A XA + LXi
er
XM(dia)
i
where llA = no. of the atoms A present in the molecules under consideration; XA = gram atom suscep-
H
tibility of the atom A; these are called Pascal's atom constants; Xi = constitutive correction for the
i-th type bond in the molecule.
k
Determination of XM fOf the members of a homologous series indicates that contribution of a

lic
CH2 group is -11.7 x 10-6 mol- l cm 3 , i.e. XM values for the successive members differ by 11.7 x
10-6 mol- l cm 3 • By using the XM value of H as -2.93 x 10-6 mol- l cm3, the XM value of C can be
C
computed.
XM(C) + 2XM(H) = -11.7x 10-6
or, XM(C) + 2 x (-2.93 x 10-6 ) = -11.7 X 10-6
or, XM(C) = (-11.70 + 5.86) x 10-6 = - 5.84 X 10-6 mol- l cm 3
The best average value is -6.0 x 10-6 mol- l cm 3 .
To obtain the XM(dia) values in SI unit from the values in CGS or Gaussian system, we can apply the
following relations:
4n x 10-6 XM(dia) (in CGS) = XM(dia) (in SI).
XM(dia) (in CGS) is expressed in the unit cm 3 mol- 1

and XM(dia) (in SI) is expressed in the unit m 3 mol-I.
The molar diamagnetic susceptibilities of some atoms, bonds, metal ions and ligands are given in
Table 8.11.1.
Table 8.11.1a Pascal's constitutive corrections (in CGS unit) for different bonds
ry
Constitution/Bond Mia Constitution/Bond Mia
ra
(10-6 em3 mol-I) (10-6 em 3 mol-I)
ib
C (ring) -0.24 C=N +8.15
C=C +5.50 C==N +0.80
yl
C==C +0.80 N=N +1.90
N=O +1.70
m
Benzene ring -6 x 0.24 = -1.44 C=C-C=C 10.6
he
C (shared by two rings) -3.07
lc
Table 8.11.1b Molar diamagnetic susceptibilities of some atoms, ions and ligands (Values given in CGS unit)
ea
Atom IonILigand
H -2.93 Ag+ -24.0

th
C -6.00 Ba 2+ -32.0
o (alcohols, ethers) -4.61 Co 2+ -12.8
e/
o (ketones, aldehydes) +1.73 Cd 2+ -22.0

Mg 2+ -3
t.m
O 2 (carboxylate) -7.95 Be 2+ -0.4

N (open chain) -5.57 Cr3+ -11
N (monoamide) -1.54 Mn 3+ -10
N ( diamide, imide) -2.11 Mo 3+ -23
e
F -6.3 Mo 5+ -12
er
CI -20.10 y 4+ -12
Br -30.60 Fe 2+ -12.8
H
I -44.6 Ni 2+ -12.8
S -15.0 Mn 2+ -14.0
k
p -26.3 Cu 2+ -12.8
lic
Se -23 CI- -26.0

As(II!) -21 Br- -36.0
1-
C
As(Y) -43 -52

coj- -24.0
CIO; -34.0
N03- -20.0
sol- -40.0
OH- -12.0
NH4+ -11.5
CH 3C0 2- -30
CN- -18
CNS- -35
1108 FUNDAMENTAL CONCEPTS OF INORGANIC CHEMISTR'v
Illustration to calculate Mia for some ligands
.© N
i.e. CsHsN (pyridine): .©J
ry
Atom Contributions Atom contributions
5C = -5 x 6 x 10-6 em 3 mol- I 6C = -6 x 6 x 10-6 em 3 mol- I
ra
5H = -5 x 2.93 x 10-6 em 3 mol- I 6H = -6 x 2.93 x 10-6 em 3 mol- I
IN (ring) = -4.61 xl0-6 em 3 mol- I Benzene ring = -6 x 0.24 = -1.44 x 10-6 em 3 mol- I
ib
Total = -49.26 x 10-6 em 3 mol- I (constitutive contribution)
Total XM(dia) = -55.02 X 10-6 em 3 mol- I
yl
Constitutive Contributions
5C (ring) = -5 x 0.24 x 10-6 em 3 mol- I (ef experimental value
m
= -1.20 x 10-6 em 3 mol- I = -55 x 10-6 em3 mol-I)
6 3
XM(dia) = -(49.26 + 1.2) x 10- em mol-
I XM(dia) = -4n x 55 x 10- x 10- m mol-
6 6 3 I
he
6 3
= -50.46 x 10- em mol- I 12 3 I
= -690.8 x 10- m mol- (SI system)
(ef experimental value
J=/\==L
lc
o--~-:H H:=O_~
= -49 x 10-6 em3 mol-I)
ea
XM(dia) = -4n x 50.46 x 10- x 10- m mol- I
6 6 3
= -633.8 x 10- 12 m3 mol- I (SI system) •
• ©(CH=N"---r
th
H2 Salen
2 N ,N'-ethylenebis(salieylideneimine)
e/
Atom Contributions
OH /c~
16C = -16 x 6 x 10-6 em 3 mol- I
t.m
HO 0
(Salicylidineglycine) 16H = -16 x 2.93 x 10-6 em 3 mol- I
Atom Contributions 20 = -2 x 4.61 x 10-6 em3 mol- I
9C =- 9 x 6 x 10-6 em3 mol- I 2N = -2 x 5.57 x 10-6 em3 mol- I
e
9H = -9 x 2.93 x 10-6 em 3 mol- I Total = -163.24 x 10-6 em3 mol- I

er
IN = -5.57 x 10-6 em3 mol- I Constitutive Contributions

O2 (earboxyl~te) = -7.95 x 10-6 em 3 mol- I 12C (ring) = -12 x 0.24 x 10-6 em 3 mol- I
H
o (alcohol) = -4.61 x 10-6 em3 mol- I 2 x C=N = +2 x 8.15 x 10-6 em 3 mol- I

Total = -98.50 xl0-6 em3 mol- I Total = +13.42 x 10-6 em 3 mol- I
k
6
Constitutive Contributions XM(dia) = (-163.24 + 13.42) x 10-
lic
6C (ring) = -6 x 0.24 x 10-6 em 3 mol- I = -149.82 X 10- em mol- I

6 3
1 x C=N = +8.15 x 10-6 em 3 mol- I (ef experimental value = -182 x 10-6 em3 mol- I
C
Total = +6.71 x 10-6 em 3 mol- I

XM(dia) = (-98.50 + 6.71) x 10- em mol-
6 3 I
= -91.79 x 10-6 em3 mol- I
In SI unit: XM(dia) = 4n x 10-6 x
-91.79 X 10-6 m 3 mol- I
= -1152.9 x 10- 12 m 3 mol- I
(experimental value is not available as the free ligand being unstable cannot be isolated)
NOTE: The experimental and calculated values of XM(dia) are not always in good agreement.
Illustration to calculate Mia of a complex

• (NH4)2CO(S04)2 . 6H 20
2 2
Mia = Mia of (2NH4+ + lC0 + + 2S04 - + 6H 20)
= (-2 X 11.5 -12.8 - 2 X 40 - 6 X 13) X 10-6 cm3 mol- I
= -193.8 X 10-6 cm 3 mol- I (CGS system)
Mia = 4n X 10-6 X - 193.8 X 10-6 m mol- I = 2434.1 X 10- 12 m 3 mol- I (SI unit).
3
ry
• [Cu(bigH)2]CI 2 . 2H20
2
ra
Xdia = Mia of (2 bigH + lCu + + 2CI- + 2H 20)
= (-2 X 60 - 12.8 - 2 X 26 - 2 X 13) X 10-6 cm3 mol- I
ib
= -210.8 X 10-6 cm3 mol- I (CGS unit)
6 3
Mia = 4n X 10-6 X - 210.8 X 10- m mol- I
yl
= -2647.6 X 10- m mol- (SI unit)
12 3 I
m
Table 8.11.le Diamagnetic susceptibilities (experimental values in COS unit) of some common ligands
he
Ligand %dia (10-6 cm3 mol-I) Ligand
Water
Ammonia
-13
-18 Pyridine
lc
Acetylacetonate -52
-49
ea
Ethylenediamine -46 Oxinate -86
Propylenediamine -58 Bipyridyl -105
Glycinate -37 1, 100Phenanthroline -128
th
Oxalate -25 Biguanide -60

Ethylene -15
e/
Hydrazine -20
Benzene -55
t.m
When the ligands are not stable in free condition, their Mia values can be calculated by using the
Pascal's constants.
8.12 EXPERIMENTAL PROCEDURE FOR DETERMINATION OF MAGNETIC

e
SUSCEPTIBILITY BY GOUY'S BALANCE METHOD

er
Theory: A thin cylindrical glass tube filled with the sample upto a certain height is vertically suspended
H
from the beam of a sensitive balance (Fig. 8.12.1) in a draught free enclosure in such a way that the
bottom end of the tube remains in a strong magnetic field while top end of the tube remains in an almost
zero field. Usually, an electromagnet having a constant magnetic field (H) of the order of (5 - 10) X 103
k
gauss is used. The weight of the sample is taken with the field on and with the field off. Similar
lic
determinations of the empty tube are taken for its diamagnetic correction.
From the experimental set-up, it is evident that the sample remains in a nonhomogeneous magnetic
C
field where the bottom end of the tube experiences the highest field (Hmax ) and top end of the tube
experiences the minimum field strength (Ho). Thus to find out the total force experienced by the sample,
the force (dF) experienced by the small volume element (dV) of the sample is to be inegrated in the
range H max to H o.
If I is the intensity of magnetisation in the sample, then from the definition of I, we can write:
I = magnetic moment per unit volume of the sample = XvH; (Cf. ~ =Xv J
i.e. magnetic moment in the volume element dV = XvHdV
The magnetic moment acts in the direction of the field.

The force experienced by the sample of volume element dV having the volume susceptibility Xv is
given by:
ry
ra
ib
yl
m
he
lc
ea
th
e/
N S
t.m
( Magnetic Field )
------------------------------
------------------------------
e
------------------------------
er
Fig. 8.12.1 Gouy magnetic balance

H
dH
where "d; denotes the field gradient.
k
If A is the cross-section of the sample and dx is the height of the small volume element (dV), then
lic
we have: dV = Adx, and

C
dF = HXvAdx( : ) = HXvAdH
It leads to:
H max H max
F = J dF = J Xv AH dH
Ho Ho
= Xv A "21 (2
H max - Ho
2)
where Hmax and Ho are the limits of the magnetic field.
MAGNETOCHEMISTRY: MAGNETIC PROPERTIES OF METAL COMPLEXES 1111
Gram susceptibility (X g ) and volume susceptibility (Xv) are related as follows:
Xg Xv, p = d
=- ·
enslty.
p
It leads to: F=X II AP"21 (2

Hmax-H O2) -XIIAPX"2Hmax,
_ 1 2 (neglectmgH
. o2) .
ry
The density can be expressed as:
ra
mass (m) m m
p=
volume area (A) x length (I) Al
ib
m
yl
or, Ap=-
I
m
Thus we get: F = XII ( 7)~(H~ax - H~) <= XII (~ )H~ax, (neglecting H~)
he
21F
It leads to: Xg = - - 2 - and,
mH max lc
ea
21F m 2F
Xv =Xi'p=~x Al = AH2
m max max
th
F is obtained from the change of weight of the sample in the magnetic field.
Therefore,
e/
21 x change in the weight of the sample

Xg = 2
t.m
mHmax
21 x ~w x 981 ( =981 -2 )
2' g cm s
mass of the sample x H
e
21F x M 21 x ~w x 981 x M (CGS )

er
i.e. XM = 2 = 2 ' system

mHmax mH max
H
(M = molecular mass of the sample)

F can be expressed in terms of Xv by using the following relations:
k
lic
XM =( ;)XV =(Molar volume)xv

C
Xv -
_ XM _ XM _
- - - - -2- -
2F _ 2~w x 981 (CGS system )
i.e. Molar volume VM AHmax ~ 2
AHmax '
2~w x 981
or, XM= 2 X(VM),(CGSsystem).
AHmax
To determine the XM value of an unknown substance (say X~), it is required to use a standard sample
whose XM and VM values are known in the same Gouy balance under the identical connections. Then it
will lead to the following working relation (in CGS system).
. st _ 2~wst g (V st ). sa _ 2~wsa g (V sa )
XM l.e. XM - 2 M' XM - 2 M
AHmax AHmax
sa sa sa
X - -
--.l:L ~Wsa
- --M.- . or Xsa - Xst (~wsa
st
[v J - - )[ --M.-
V J
or, X~ - L\w V;;' , M - M ~wst V;;'
ry
Here, the superscript 'st' and 'sa' stand for the standard sample and unknown sample respectively.
By using the above relations, we can calculate XM from which X/JIT (i.e. corrected XM) is obtained as
ra
follows:
XM' i.e. XM (observed value) = Xparamagnetism + XTIP + Miamagnetism
ib
= Xpara + XTIP + Xdia
yl
Xpara = XMo = XM -
rr
diamagnetic correction - TIP
m
By using Curie equation we get:
= 2.83~X(;r' T B.M. XM in CGS unit.
he
Jlobs
1 B.M. = 9.27 x 10-21 erg G- I

Curie-Weiss equation leads to: lc
Jlobs = 2.83~Xc,:;rr (T - e) B.M.
ea
In terms of SI unit, it can be shown:
th
F =~XvA(H~ajJlo)' Jlo = permeability in free-space = 41t X 10-7 N C-2 s-2

2 .
e/
'VvA(HJl~oax ]" or, Xv --

t.m
or, 2F = A; A ---.!:L
2F H 2 -_ XM
V
max M
2FJlo 2~wg JloVM

=
e
or, XM = - - 2 - XVM 2
AHmax AH max
er
(g = 9.81 m S-2 = acceleration due to gravity in SI unit)

is obtained as follows:
H
J.lobs
Jlobs = 797.6~Xc,:;rrT B.M. or, Jlobs = 797.6~XM (T -e) B.M.

k
Procedure: The instrumental calibration constant (21/J-!2max or AlPmax) for a particular Gouy tube and at
lic
particular field is determined by using some standard samples such as CUS04' 5H 20 (Xg = 5.92 X
10-6, CGS system), Hg[Co(NCS)4] (X g = 16.44 X 10-6 , CGS system) whose magnetic susceptibility is
C
known correctly. Then the same tube is used after cleaning for the sample (under investigation) in the
same instrument under the identical conditions.
Let us illustrate the procedure for a particular sample.
mass of the empty tube (when the field off) = WI
mass of the empty tube (when the field on) = W2
WI ) W2 and diamagnetic correction for the tube = (WI - W2)
mass of the (tube + sample) (when the field on) = W3
mass of the (tube + sample) (when the field off) = W 4
(W4 ( W3 when the sample is paramagnetic).
Thus the mass of the sample taken is given by:

m = (W4 - WI)
The actual force experienced (downward) by the sample is:
F = [(W3 - W4) + (WI - W2)]g = ~wg, g = 981 cm S-2
Therefore, we can write (in CGS system):
ry
Xg -- ( - 2 ~wg
2l - - _ 2~wg
- , or Xv - - - 2 -
H max m AHmax
ra
(+J A~ax is obtained from a standard sample whose X
ib
The instrumental parameter, or g or
H max
yl
Xv is kJ?own. Then Xg or Xv is obtained for an unknown sample by using the instrumental parameter.
m
The diamagnetic corrections are obtained from Pascal's empirical rules and TIP is obtained from
Van-Vleck's equation for the 2nd order Zeeman effect.
he
Drawbacks of Gouy method: Anisotropy ofthe crystals and non-uniformity in packing are the main
sources of error in this method. These errors can be minimised by proper grinding of the sample to fine
powder. If the solutions are used then the errors are also minimised.
lc
ea
ILLUSTRATIVE EXAMPLES:
Example 1: Calculation of J.lobs for [Cu(bigH)2]CI 2· 2H 20 (M = 372.5) from the followinr data.
th
Temp. 293 K; WI = mass of the empty tube (magnetic field off) = 10.72302 g
W2 = mass of the empty tube (magnetic field on) = 10.72246 g
e/
i.e. diamagnetic correction for the glass = (WI - W2) g

W3 = mass of the (tube + standard sample Hg[Co(NCS)4]) (magnetic field on) = 11.76296 g
t.m
W4 = mass of the (tube + standard sample Hg[Co(NCS)4]) (magnetic field off) = 11.73996 g
Mass of the standard sample (m st ) = W4 - WI
= (11.73996 - 10.72302) g
e
= 1.01694 g
er
Actual force experienced by the standard sample is:

Fst = [(W3 - W4) + (WI - W2)]g dyne
H
= [11.76296 - 11.73996) + (10.72302 - 10.722460]g dyne

= (0.02300 + 0.00056)g dyne
k
=0.02356g dyne; g = 981 cm S-2

lic
Xg for Hg[Co(NCS)4] = 16.44 x 10-6 (CGS unit).

C
st = (~).!.E- i.e. 16.44 x 10-6 = (~) x 0.02356g

Xg H 2 m st H 2 1.01694
Mass of the (sample + tube) (magnetic field off) = Ws = 11.05913 g
Mass of the (sample + tube) (magnetic field on) = W6 = 11.06013 g
Actual force experienced by the sample is given by:
F.m = [(w 6 -WS)+(w I -w 2 )]g dyne = [(11.06013 - 11.05913) + (10.72302 - 10.72246)]g dynes
=0.00156g dyne, g = 981 cm S-2

Mass of the sample (m sa ) = (ws - WI) g = 11.05913 - 10.72302 = 0.33611 g
sa
g
=(~) Fsa =(~)x 0.00156g
X H 2 mm H2 0.33611
0.00156 1.01694
---x---
ry
0.33611 0.02356
ra
sa = 16.44 X 10-6 X 0.00156 X 1.01694
or, Xg 0.33611 0.02356
ib
= 3.2935 X 10-6 (CGS unit)
XJ:/ = X~ x M = 3.2935 x 10-6 x 372.5 ::::: 1227 x 10-6 (CGS unit)
yl
i.e.
i.e. XtJ::::: 1227 X 10-6 mol- l cm 3
m
For the given complex, the diamagnetic correction (Pascal's rule) ::::: -211 X 10-6 mol- l cm 3 (cf Sec.
he
8,11, illustration), and TIP = + 50 X 10-6 mol- I cm 3 . The said diamagnetic correction is obtained as
follows:
diamagnetic correction for one Cu 2+, two biguanides, two CI- and two H 20 =-( 12.8 + 2 x 60 +
2 x 26 + 2 x 13) X 10-6 ::::: -211 X 10-6 mol- l cm 3 (cf Sec. 8.11).
lc
ea
It leads to:
X~rr(sa) = [1227 - (-211) - 50] x 10 6 mol- I cm 3
th
= 1388 x 10-6 mol- Icm 3

e/
ll~ff = 2.83J1388 x 10-6 x 293 B.M. = 2.83 x 637.7 x 1O-3 B.M. = 1.80 B.M.
t.m
Example 2: 0.2 Inol dm- 3 solutions of the ions [Co(NH 3)6]3+ and [CoF6]3- were placed (Temp. 298 K)
separately in 1 Cln diameter test tubes suspended in a Gouy balance in presence of a magnetic field
8,000 G. Calculate the mass enhancement in two cases when the field is on. (Consider the J.lspm only)
e
Solution: [Co(NH 3 )6]3+ i~ a low spin complex (t~K) and it is a diamagnetic substance (ignoring TIP).
er
Thus it will be slightly repelled (i.e. its mass will be slightly decreased) when it will be placed in a Gouy
balanc~ with the magnetic field on. On the other hand, high spin [CoF6]3- (tigei) having 4 unpaired
H
electrons will show the paramagnetism and it will be attracted when placed in the Gouy balance with
the magnetic field on.
k
~;n ], (Gaussian system)

lic
XM = N A (
3k B T
C
~m' = ~spin-only = 2~S(S + 1) ~B
i.e. XM =~(2JS(S+I)IlBt
3k T B
4 x (9.274 X 10-21 erg G- 1 )2 x (6.023 x 1023mol~l) ( ) ('T" _ 250C)

= 16 t
S S + 1 , lemp.-
3 x (1.38 x 10- erg K- ) x298 K
= 1.68 x 10-3 erg 0-2 mol- 1 {S(S + I)}
= 1.68 x 10-3S{ (S + I)} mol- I cm3

[G = gl/2 cm- l12 S-I, erg = dyn cm, dyn = g cm S-2]
4
For 4 unpaired electrons: S =- =2
2
It leads to:
ry
XM = 1.68 X 10-3 x 2 x 3 mol- I cm 3
= 10.08 x 10-3 mol- I cm 3 .
ra
Concentration of the solution is 0.2 mol dm- 3 . Thus 2 mol of the substrance remains in 10 dm3, i.e.
molar volume (VM) = 5 dm 3 mol- I = 5 x 103 cm3 mol-I.
ib
We have the relation:
yl
F=C~w)g=X H2(mJ=(kJH2(mJ=~AX H 2. p=~
m
2l P g2/ 2 v ' Ai
= cross-sectional area of the tube = n?
he
A
r = 0.5 cm.
lc m
~w = mass ehancement when the magnetic field on, p = Al
ea
or, F = (tlw)g = (Xv: AlJH
2
(~ J= (Xv AH2 }/2;
th
XM = Mx X = M( X; J=(; JXv = (Molar volume) x Xv

e/
g
t.m
- XM XM
or, Xv-
Molar volume VM
By using the above relations, we can write:
e
F=(tlw)g=~XvAH2 =~(XM JAH 2 , (A=nr 2)

er
2 2 V M
~w=_1 (XM JAH 2, H=8,000 G

H
or,
2g VM
k
l
=( 2x981cms-
1 Jx(10.08XIO- mOl- cm
3 3
](22 xo.52cm2Jx(8,000 G)2
lic
2 5xI0 cm mol- 3 3 1
7
C
10.08 x 3.14 x 0.5 x 0.5 x 64 x 10 6 x 10-6 2 G2

---------------cm s = 0.051 cm S"') G 2
2 x 981 x 5
= 0.051 g, [G = gl/2 cm- l12 S-I]
When the solution is placed in the Gouy tube, its mass will increase by 0.051 g when field (H =
8,000 G) is on.
In terms of SI units, the problem can be solved as follows:
XM = 4n (10.08 x 10-9 ) mol- I m3 .
Jlo = 4n x 10-7 H m- I = 4n x 10-7 N C- 2 S2
g=9.81ms- 2
A = 1tr 2 = e;) x (0.005 m)2
VM = Molar volume = 5 x 10-3 mol- I m3

H = 8000 G = 8000 X 10-4 T = 0.8 N C- I m- I s.
ry
The working formula is:
ra
~w=_1
2
(XMJA(H J
ib
2g V Jlo M
yl
Other methods of magnetic susceptibility determination
m
Besides the Gouy method, other methods like Faraday method, NMR method (with the temperature
variation facility) are known. SQUID (superconducting quantum interfering device) is the modem
he
technique to determine the magnetic susceptibility.
8.13 SPIN-ORBIT COUPLING CONSTANTS: SPLITTING OFTHE ENERGY LEVELS:

lc
ea
LANDE INTERVAL RULE (cf. Sec. 7.7.4)
(A) Spin-orbit coupling constant: To measure the strength of interaction between the spin and orbital
th
angular momenta, spin-orbit coupling constants S (ZETA) and A are commonly used. The first one
(which gives the measure of the strength of the interaction between the spin and orbital angular momenta
e/
of a single electron of the configuration) is used for a single electron while the second one is used for
t.m
the many electron systems characterised by the Russel-Saunders terms. These are given below:
2 2
Zeffe h
~= 2 2 2 3' (CGS system)
81t mec r
e
er
') ')
JlOZeff e - h -
= 2 2 3 ' (SI system)
321t me r
H
and A = ± S/2S = ± sIn, S(a positive quantity); n = number of unpaired electrons.

k
+ sign of A for a less than half-filled shell; - sign of A for a more than half-filled shell.
lic
Number of unpaired electrons in free ions: In the free ions, all the d-orbitals are degenerate and
in such cases, number of unpaired electrons can be computed as usual.
C
d X (x = 1, 2, 3, 4, 5) (free ion): No. of unpaired electrons (n) = x and A is positive; for d 5 (L = 0),
no spin-orbit interaction occurs and A is redundant for d 5 •
d X (x =.6, 7, 8, 9, 10) (free ion): No. of unpaired electrons (n) = 4, 3,2, 1,0 for x = 6,7, 8,9, 10
(respectively); A is negative; for d 10 (L = 0, S = 0), A is redundant.
Number of unpaired electrons in complexes: In the presence of crystal fields, degeneracy of the
d-orbitals is lifted. In an octahedral crystal field, the five d-orbitals split into the two sets - t 2g set
consisting of the di .,., dy: and d:x orbitals and eg set consisting of the d x2 _.'.2 and d _2 orbitals.
In a tetrahedral field, the d-orbitals are split into the t2 and e-sets.
For the high-spin octahedral and tetrahedral complexes of transition metal ions, the number of
unpaired electrons is the same as in the corresponding free ion and A will be positive for the number
of electrons less than 5 while A will be negative for the number of electrons greater than 5. In a strong
octahedral crystal field, to determine the number of unpaired electrons, the t2g and eg sets are to
be considered as the separate shells. It is illustrated below:
dX and 12; (x = 1, 2, 3): No. of unpaired electrons = x; A bears a positive sign.
ry
Low spin (]X and 12: (x = 4,5, i.e. more t,han half-filled): No. of unpaired electrons = 2 and 1 for x =
4 and 5 respectively; A bears a - sign. These are illustrated in Table 8.13.1.
ra
Effect of oxidation state: It is evident (ef Table 8.13.2) that the spin-orbit coupling constant
increases with the increase of positive oxidation state, more correctly Zeff and decreases with the increase
ib
of radius (r).
yl
Table 8.13.1 Spin-orbit coupling constants (in em-I) for the first transition metal ions (free ions)
m
~ (em-I)
Ion (dO) Ground state Ground state "- Ground state "-
he
term (weak term (tetrahedral (± ~n)(a) term (strong (= ± ~n)(a)
Ohfield) field) (in em-I) (in em-I) Ohfield)
Ti 3+(d 1)
y3+(~)
155
210
2T2g (ti g e~)
3T1g (t~g e~)
2E
3A 2 (e 2 tr)
lc
(e 1 tr) +155
+105
2T2g (t1 g)
3T1g (t~g)
+155
+105
ea
y2+(d3) 170 4A 2g (qg e~) 4T1 (e 2 t1) +57 4A 2g (t~g) +57
Cr3+(d3) 275 4A 2g (qg e~) 4T1 (e 2 t1) +92 4A 2g (t~,,) +92
th
Cr2+(tf) 230 5Eg (t~g ei) 5T2 (e 2 t}) +58 3T1g (ti g) -115
Mn 3+(tf) 5T2 (e 2 t})
e/
355 5Eg (tig ei) +89 3T1g (ti g) -178

Mn2+(~) 300 6A 19 (t~g e;) 6A 1 (e 2 t1) 2T2g (~g) -300
*
t.m
Fe3+(~) 460 6A 1g (d g e;) 6A 1 (e 2 ti)

* 2T2g (~g) -460
Fe 2+(£!» 400 5T2g (tig e;) 5E (e 3 t1) -100 lA lg (t~,,) *
C0 3+(£!» 580 5T2g (rig e;) 5E (e 3 t1) -145 lA Ig (t~g) *
e
C0 2+(d') 515 4T1g (~g e;) 4A 2 (e 4 t1) -172 2Eg (t~g ei) -515
Ni 2+(tf8) 3T1 (e4 ti)
er
630 3A 2g (t~g e;) -315 3A 2g (t~g e;) -315

Cu 2+(tfJ) 830 2Eg (~g ei) 2T (e 4 ti)
2 -830 2Eg (t~g ei) -830
H
i,
(a) n = number of unpaired electrons to calculate A. For t 2:, n = 2 and negative sign for A; for t 2 n = 1 and A becomes
negative.
k
* For L or S = 0, A becomes redundant because no spin-orbit interaction occurs.

lic
Table 8.13.2 Single-electron spin-orbit coupling constant (~in em-I) for some transition metal ions (free ions)
C
Oxidation Sate
Element 0 +1 +2 +3 +4 +5 +6
Ti 70 90 120 155
y 90 135 170 210 250
Cr 135 180 230 275 350 380
Mn 185 250 300 355 420 475 550
(Contd.)
Fe 270 335 400 460 520 580 660

Co 400 450 515 580 650 720 800
Ni 560 630 705 800 870 950
Cu 830 890 950 1025 1120
Zr (300) (400) (500)
ry
Mo (670) (825) (860) (900)
Ru (1260) (1400) (1500)
ra
Rh 940 1060 1220 (1360) (1570) (1730) (1960)
ib
Values within the parentheses are. the theoretical estimates.
(B) Factors controlling the magnitude of spin-orbit coupling constant: These are discussed below.
yl
• Effect of effective nuclear charge (A oc Zeff): Zeff increases with the increase of atomic number in
m
a period and in a group for the d- andf- block metals. This is why, for the late members of a series, the
value of A is relatively higher. Similarly, for the heavier congeners in a group, A is higher. For the
he
lanthanides and actinides, because of the low-shielding (n - 2)f and (n - l)d electrons, Zeff increases and
consequently the spin-orbit coupling constant becomes relatively higher than that of the d-block metal
ions (cf Tables 8.13.1-4). lc
ea
'A (complex)
Table 8.13.3 Ratio of A( . ) « 1) in some representative complexes Note: The ratio less than unity
free Ion
th
indicates the covalence in the metal-ligand bond, i.e. nephelauxetic effect

e/
A(complex) A(complex)
Complex Complex
t.m
A(free ion) A(free ion)
[Cu(OH 2)6F+ 0.78 [Cr(en)3]3+ 0.48

[Cu(NH 3)4F+ 0.48 [Cr(CN)6]3- 0.35
e
[Cr(OH 2)6]3+ 0.60 [Ni(OH 2)6F+ 0.83

er
[Cr(NH 3)6]3+ 0.48 [Ni(NH 3)6F+ 0.65

H
Table 8.13.4 Single-electron spin-orbit coupling constant for the trivalent lanthanides (4j)
k
Ion: Ce(III) Pr(III) Nd(III) Pm(III) Sm(III) Eu(III) Gd(III) Tb(III)

lic
n: 1 2 3 4 5 6 7 8
C
S(em-I): 645 800 900 1200 1415 1620
Ion: Dy(lll) Ho(lll) Er(lll) Tm(lll) Yb(lll)
n: 9 10 11 12 13
S(em-I) 1820 2080 2360 2800 2940
• Effect of orbit radius ( A oc?1 ) : For a particular metal ion, with

'/
the increase of oxidation state,
the size of the metal ion decreases (i. e. r decreases) and Zeff increases (due to less screening). Consequently,
A increases with the increase of oxidation state for a particular metal ion. Thus, A(Fe 3+) ) A(Fe 2+);
A(C0 3+) ) A(C0 2+) (ef Table 8.13.1).
• Periodic position of the metal ions: For the heavier congeners among the d-block metal ions, the
size does not practically increase but Zeff increases. This is why, A increases for the heavier congeners.
A: Pt 2+ ) Pd 2+ ) Ni 2+; OS3+ ) Ru 3+ ) Fe3+.
• Nephelauxetic effect: In a complex, electron cloud expansion leads to an effective increase in
ry
orbit radius. Thus in a complex, A decreases compared to that of the free ion (ef Table 8.13.3). This
decrease occurs by 20 - 25%. Spin orbit coupling constant (A) in a complex may be obtained from the
ra
ESR data or magnetic data (ef Sec. 8.16).
(e) Splitting of energy levels due to spin-orbit coupling and energy values of the components
ib
in a multiplet (cf. Fig. 7.9.3.1): According to L - S coupling, we get the Russel-Saunders terms .as
yl
follows:
Spin multiplicityL) = 2S+ IL)
m
where i = IL + SI to IL - SI at every integral step. For example, 3F term (L =3, S = 1) splits into the states,
3F2 , 3F3 and 3F4 through the spin-orbit coupling process (ef Fig. 7.9.3.1).
he
Thus the successive i-values differ by unity. Each i-value corresponds to a particular energy state.
The different i-levels (ranging between IL + SI to IL - SI) of a particular Russel-Saunders term constitute
lc
a multiplet. Thus the 3F2 , 3 F3 and 3F4 states originated from the 3 F term constitute a multiplet. The L
anq S vectors act at different angles to give the different resultant J vectors. Consequently it will lead
ea
to different i values (quantum numbers). Spin-orbit interaction energy of a particular i-value is given by:
AL · S = ALS cos (L, S) where we have the following relations (ef dot product of vectors and
th
Appendix-VIII A,B):
J2 = L 2 + S2 + 2LS cos (L, S); J is the resultant vector arising from the Land S vectors acting at (L,
e/
S) angle.
t.m
h
e
Expressing Land S vectors in the unit of - , we get:

21t
er
ALS cos (L, S) = ~A [i(i + 1) -

L(L + 1) - S(S + 1)] = E) = Energy of a i-level with respect to that
H
2
of the unsplit Russel-Saunders term.
k
Now let us consider the energy values of two successive levels, say i and i + 1.
lic
t1E), )+1 = E)+I - E)
=!A[ (J + I)(J + 2) - J J
C
L(L + 1) - S(S + 1) -!A[J (J + 1) - L(L + 1) - S(S + 1)

2 2
=!A[(J + I)(J + 2) -J(J + 1)J = A(J + 1) = A x larger J value.

2
The energy difference between the successive i levels is given by:
E), ) + I = E) - E)+I = A(i + 1).
This is referred to as the Lande Interval rule which states that the energy difference between the
successive i-levels is given by the product of the spin-orbit coupling constant and the higher i-value.
This magnitude of the energy difference gives the measure of multiplet width.
In presence of an external magnetic field (of strength H), each J level symmetrically splits into 2J+ 1
sublevels characterised by the MJ values which are given by +J to -J at every integral step. This
splitting into (2J + 1) sublevels for each J level leads to a submultiplet having the multiplicity or
sublevels 2J + 1. The energy of a sublevel characterised by MJ is given by:
EM = gf3MJH
J
eh
ry
where H = field strength of the applied magnetic field; ~ = - - and g is called the Lande splitting
41tm e c
ra
factor and it is given by:
ib
=1+ J(J+l)+S(S+I)-L(L+l)
g 2J(J+l)
yl
The energy difference between the successive MJ levels is given by gf3H and it is constant for a
m
particular J-value.
(D) Barycentre rule and degeneracy of states: The splitting pattern of the energy levels is shown
he
in Figs. 7.7.4.4, 7.9.3.1 (Chapter 7) and Fig. 8.14.1.
Multiplicity of a particular J-Ievel (i.e. a component of a multiplet) is given by 2J + 1 determined
lc
by the Mrvalues (ranging from +J to -1). During the splitting of a Russel-Saunders term to produce a
multiplet, the barycentre rule is maintained. It is illustrated for the 3p tenn (tP and t!' configurations).
ea
3p(d2): [(2 x 2 + 1) A] + [(2 x 1 + 1) (-A)] + [(2 x 0 + 1)(-2A] = 5A - 3A - 2A = 0 }(Cf. Figs.
3 8 8.14.1,
th
P(d): [(2 x 0 + 1) (2A)] + [(2 x 1 + 1) (A)] + [(2 x 2 + 1)(-A] = 2A + 3A - 5A =0 7.9.3.1)

e/
The degeneracy is also maintained. A Russel-Saunders tenn is (2L + 1)(2S + 1) fold degenerate and
each J-Ievel is (2J + 1) fold degenerate. Thus for the 3P tenn we have:
t.m
(2L + 1)(2S + 1) = (2 x 1 + 1) (2 x 1 + 1) = 9;
L (2J + 1) = (2 x 2 + 1) + (2 x 1 + 1) + (2 x 0 + 1) = 5 + 3 + 1 = 9 (cf Fig. 7.9.3.1)
8.14 PARAMAGNETISM ANDTHERMAL ENERGY
e
For the multielectron systems, in defining a particular state (Russel-Saunders Term), the J-value
er
(= IL + SI to IL - SI) must be mentioned. For the ground state term, the J-value can be detennined by
the Hund's rule. For a particular Russel-Saunders tenn, all the possible J-values ranging from (L + S)
H
to (L - S) constitute a multiplet in which each J-value corresponds to a particular energy state. For
example, 3Fb 3F3 , 3F4 for the 3F-term produce a multiplet. Energy difference between the two successive
k
J-Ievels is known as the multiplet width. The magnitude of multiplet width is detennined by the Lande
lic
Interval rule.
Multiplet width = ~J, J+l or ~J+l, J = E J - E J+1 = A(i + 1).
C
The magnitude of multiplet width detennines the relative population density at the different J-Ievels
at a particular temperature. Thus, the relative contribution towards the paramagnetism from the different
i-levels at a particular temperature is governed by the relative magnitudes of the multiplet width
(~EJ, J+l) and thennal energy (kBD. When kBT is close to the multiplet width, the population density at
the excited states is significantly high. In such cases, both the ground state and excited state contribute
to the observed magnetic properties. It happens so in the case of Sm(lll) and Eu(III). When the
multiplet width is too large compared to kBT, the magnetic property mainly originates from the ground
state because population density at the excited states is negligibly small. Depending on the relative
values of ~EJ,J+l and kBT, three distinct situations may originate:
(i) multiplet width) ) kBT, i.e. population density at the excited levels is negligibly small, i.e. ground
I-level mainly contributes to the magnetic property.
(ii) multiplet width « kBT, i.e. virtually all the I-levels are supposed to be populated, i.e. all the
I-levels contribute to the magnetic property.
(iii) multiplet width == kBT, i.e. population density at the excited levels depends on the I-value, i.e.
energy of the I-level; contribution of the different I-levels to the magnetic property depends on
ry
their relative population densities governed by the Boltzmann distribution law.
ra
'A J=2 I 2'A J=0
I ~
I
I (2J + 1) , "
ib
I
I fold degenerate "
I I
r-----
I I
yl
I
I
3 / Multiplet I
I
p " __________ _ width
m
I I
I I
.. ~ J = 1
(2L + 1) (28 + 1) \\ I I
~ ~E2. 1
I I
he
fold degenerate ""
\ \
I I
I I
\ \ = 2'A I I Multiplet
\ \ I,' width
\
\
\
\
\
\
\
\ -'A
\----r
3
lc p
( __u__uu-./
I,
ea
\ \
\ \
\ \
\ \
\ \
\ -l1li
\
th
\ \
" -2'A \ -'A ,. J = 2

e/
8
(d )
t.m
J=5
J=~
2
J=5
e
~E~, ~
er
2 2 J=3
H
J =2-
2
k
lic
~E~, ~
C
2 2
J=~
J=4 " 2 J=6
Ground
state term:
Fig. 8.14.1 Multiplet and multiplet width, !J.Ej , j+\ or !J.Ej +1. j in different cases. (a) cP configuration, (b) cr configura-
tion, (c) some representative trivalent lanthanides.
Magnetic moments for the different multiplet widths will be discussed here without any mathemati-
cal derivation. Derivations of the relations are given in Appendix-VIII at the end of this Chapter.
A. Case I: Multiplet width (till), }+1) larger compared to kBT (cf. Appendix VIII A)
We know: ~J, J+I = multiplet width = A(I + 1).
In such cases (i.e. ~EJ. J+I » kBn, the spin-orbit coupling constant is quite high and consequently, the
Land S vectors interact strongly and I appears as a good quantum number. In such cases, the higher
ry
I-levels are negligibly populated and only the ground I-level contributes to XM.
ra
The magnetic susceptibility developed from the ground I-state is given by:
N N
XM = _A_ g;B 21(1 + 1); simply it is: XM = _A_ g 2 B21(1 + I)
ib
3k BT 3k BT
yl
The corresponding magnetic moment (JlJ) is given by:
IIII = glP~J(J + I) ;simply it is: III = gP~J(J + I) i.e. III = g~J(J + I) B.M·I
m
he
A-~ d (. . I )-1 I(I+I)+S(S+I)-L(L+I)
where I-' - an gJ l.e. sImp y g - + ()
41tm e c 21 I + 1
Here the magnetic moment mainly arises from the ground state specified by a particular I-value and
lc
ea
the spin-orbit coupling constant is so high that the other states (i. e. the higher energy levels) are not
thermally accessible. The heavy transition metal ions and most of the lanthanide ions (except Sm 3+ and
Eu 3+) follow this pattern. The magnetic moment developed from a particular I-value in this fashion is
th
considered as the magnetic moment due to the 1st order Zeeman effect according to
Van-Vleck equation.
e/
The first-order Zeeman effect for a state defined by a particular I-value gives the 21+ 1 sublevels
t.m
(i.e. splitting of a I-level by the magnetic field H) characterised by the MJ-values (-1 to +1) and energy
of a particular sublevel is given by (cf Fig. 7.9.3.1): EM = MJgBH,
J
i.e. energy separation between any adjacent pair of M J values is given by: g~H.
MJ EMJ
e
Jl
(= MJg~H) (= -E/H)
er
/ +2 2g~H -2gB
H
/
/
/
/
/
/
k
/
/
+1 19~H -1gB
I
" "
lic
""
/
/
"
""
/
/
/ """
"
C
, ,---------
(,"
,........ ....
0 0 0
J=2 , ,.... .... .... ....
, , .... .... ....
Ig~H
,, .... ....
,, -1 -1g~H +1g~
,,
,,
,,
-2 -2g~H +2g~
Fig. 8.14.2 Splitting of a particular i-level (for i = 2 as an example) by an external magnetic field (H), i.e. illustration
of 1st order Zeeman effect ( E = fiR where fi denotes the projection of the magnetic moment in the direction of H).
By considering the Boltzmann distribution for the different Mlevels and X = -~(
J dE).
H dH
We can
write (see Appendix VIII 0, E for details):
ry
average magnetic moment per molecule = N A~av
ra
XM = N A X
H H
ib
+J
XM(J) = NA L M;g2~2 /k BT(21 + 1), (cf. Appendix-VIII 0, E)
yl
MJ=-J
m
he
lc
ea
th
e/
=(N Ag2~2 J 1 x 2J(J + 1)(2J + I) = ~ i~2 J(J + I)

t.m
kBT (21 + 1) 6 3k BT
21(1 + 1)(21 + 1) .
L+J 2
= , (see E)
e
cf· MJ AppendIx VIII

MJ=-J 6
er
N AJl5
H
i.e. J-lJ = g~~1(1 + 1) = g~1(J + 1) B.M.; cf XM = 3k T

B
k
nd
Note: Here we have ignored the 2 order Zeeman effect leading to TIP.
• When S = 0 (i.e. spin angular momentum = 0), 1 becomes L (i.e. J = L)
lic
and III reduces to JlL

(i. e. J.ll = J.lL) and g becomes 1. Therefore:
C
J.lL =g~L(L+l)~=JL(L+l) B.M.

• When L = 0 (i.e. no orbital angular momentum), 1 becomes S (i.e. 1 = S) and J-ll reduces to J.ls
(i.e. magnetic moment due to spin angular momentum) and g becomes 2.
i.e. Ils =g~S(S+I)~=~4S(S+I)J3=~n(n+2)~; (g=2, S=%)

i.e. Jls =In(n+2) B.M.
This is called Bose-Stoner's spin only formula. It is named after D.M. Bose and E.C. Stoner.
B. Case II: Multiplet width (dE), }+1) smaller compared to kBT (ef Appendix VIII B, E).
In such cases, coupling between the Land S vectors is insignificant (i.e. i is not a good quantum
number) and the magnetic susceptibility arises from the two sources independently which are additive, i.e.
2 2
XM =XL +Xs =NA~L NA~S ( .
- - + - - ; ef· AppendlxVIIIB,E
)
3k BT 3k BT
ry
ra
=~(f.!~ +f.!n=~[L(L+l)+4S(S+1)]
3k BT 3k BT
ib
Therefore: ~L+S = ~L(L + 1)+45(5 + 1) ~
yl
= ~L(L + 1) + 45(5 + 1) B.M.
m
If L = 0, it becomes: Jls = )45(5 + 1) B.M. (ef quenching of orbital contribution by
he
crystal field effect)
If 5 = 0, it becomes: JlL = ~L(L + 1) B.M.

In fact, under the condition, /1EJ, J+I « kBT, virtually all the i lc
levels are supposed to be populated and
each i level splits into 21 + 1 components (specified by the M J values) in presence of an external
ea
magnetic field H. Considering this aspect and statistical factors, it can be shown that
= ~L(L + 1) + 45(5 + 1)
th
I-lL s B.M.
Here it should be pointed out that in reality, there is no such system having the spin-orbit coupling
e/
constant so low that the condition, !W}, }+1 = A(] + 1) « kBT is satisfied. Theoretically, the condition
t.m
may be only attained at high temperature.

C. Case III: Multiplet width (AE), }+1) is comparable to kBT.
It happens so when the spin-orbit coupling constant (A) is of the order of kBT. In such cases, the excited
i-levels are populated and governed by Boltzmann distribution law. Then, the first-order Zeeman
e
effect for each i-level will contribute to XM according to their Boltzmann population density. By
er
considering the 1st order Zeeman effect for a particular i-level (assuming that this particular i-level is
only populated), we get:
H
XM(J) = -N-Ag J2 i ( 1 + 1) ~ 2
3k B T
k
lic
In the present case, the different i-levels will contribute to the resultant XM according to their relative
population densities. Thus the Avogadro number (NA ) is given by:
C
IL+sl
NA=NJ+N J+ 1 +·······= L
J=IL-si
NJ
Thus we can write:

IL+sl N g2 i (i + 1)~2
XM = ~ ~J-=...J _
J=tSI 3k B T ... (i)
Each i-level undergoes splitting into (2i + 1) components (specified by the MJ-values). If energy of
a particular 1-level is /1EJ (compared to the ground state i-level), i.e. it lies above the ground state by
~], then its population density is determined jointly by its multiplicity (i.e. 2J + 1 sublevels) and
Boltzmann distribution law:
NJ oc (2J + 1) exp (- ~] J' (2J + 1) gives the multiplicity of the level.

kBT
ry
=C(2J + l)exp (- ~J J. ,C = proportionality constant.
kBT
ra
ib
yl
m
or, ... (ii)
he
By using this 'value of C (proportionality constant), we can express N] as follows:
N (2J +1)exp(-~]/kBT) lc
NJ =-A- - - - - - - - -
I(2J + l)exp(-dE] /kBT)
ea
Using this value of N] in Eqn. (i), we get:
th
IL+sl
2 L g;J(J+l)(2J+l)exp(-~J/kBT) 2 [ ]
e/
X = N A~ x J;IL-si = N A~ X X (say)
M 3k T IL+sl 3k T Y'
L
t.m
B (2J + l)exp( -dEJ /kBT) B

J=IL-si
1
e
where ~ 2 =[X]
y B2,I.e.
. ~= [X]2
y B.M.
er
Therefore, magnetic moment is given by:

H
2
2
Jl = [Ig;B J(J + 1)(2J + l)exp( -dE] /k BT)]1/
k
I(2J + l)exp( -~J /kBT)

lic
Note: Here we have ignored the 2nd order Zeeman effect causing TIP.
C
We have: E J = ![J (J + 1) - L (L + 1) - S(S + 1)]A., (see Sec. 8.13)

2
~] = E] - E] (ground state) = energy of a J-Ievel with respect to that of the ground state J-Ievel.
= ~[J (J + 1) -IL - sl(IL - sl + 1)] A., assuming J(ground state) = IL - sl
It is illustrated for Pm 3 + (L = 6, S = 2, 5]4; ground level J = 4, 1st excited state J = 5).
M J =EJ ;5 -EJ ;4 =~[5X6-(4)X(4+1)]A.=5A
Lande interval rule also gives: ~J = £4,5 = 5A

gJ = g (Lande factor), (defined by 1)
Origin of the magnetic moment: The orbital and spin motion of an unpaired electron are responsible
for the magnetic moment. For an atom or ion, the resultant angular momentum vector (J) is ex-
pected to be responsible for the observed magnetic moment. It is given by:
ry
J.leff =J.lJ =gJ~J(J+l) B.M.,
ra
-1+ J(J +1)+S(S+I)-L(L+l)
gJ - 2J (J + 1)
ib
Spin-orbit coupling constant is very high for the lanthanides, actinides and heavier transition
yl
series. In such cases, J is a good quantum number and J.!J works well.
m
D. Important relations to calculate J..lefT
If the coupling between land S is inefficient, i. e. the spin-orbit coupling constant is small (as in the
he
case of 1st transition series), the orbital and spin angular momenta will contribute independently.
J.leff = J.lL+S = ~4S(S + 1) + L(L + 1)

lc B.M.,
ea
For the systems like complexes of the 1st transition series where the spin-orbit coupling constant is
small (i.e. J is a not a good quantum number), J.!L + S should work. But, crystal field effect largely
quenches the orbital contribution (i.e. L = 0) and magnetic moment is given by the following equation
th
where n = number of unpaired electrons:

e/
= J.ls = ~4S(S + 1) B.M. = )n(n + 2)

J.leff B.M. (called Bose-Stoner formula)
• Multiplet width = ~£J. J+l = A(J + 1).
t.m
(i) AE}, }+1 » kBT (i.e. A is high);

J.leff =J.lJ =gJ~J(J+l)B.M.
e
1
er
XM follows the Curie law, i.e. X oc -

T
« kBT (i.e. A is
H
(ii) AE}, }+1 small):
J.leff = J.lL+S = ~4S(S + 1) + L(L + 1) B.M.

k
(Provided, crystal field effect does not quench the orbital contribution).
lic
XM follows the Curie law

C
(iii) ~J, J+l :::: kBT, J.!eff is a complicated function of J and T.

E. Van-Vleck Equation: 1st and 2 nd order Zeeman effects (cf. Appendix VIII E)
• 1st order Zeeman effect leads to splitting of a particular J-Ievel into 2J + 1 components (specified
by the M J values ranging from -J to +1) in presence of an external magnetic field (H). These 2J + 1
components are symmetricallly distributed above and below the zeroth level, i.e. M J = O. The first order
Zeeman effect contributes to the susceptibility as given by Curie equation.
The first-order Zeeman effect is applicable for the J-Ievels which are thermally accessible, i.e. the
energy levels (E' »kBT, where E' gives the energy of a ]-level with respect to that of the ground
]-level) lying far above the ground level do not contribute to the 1st order Zeeman effect.
• 2nd order Zeeman effect allows the mixing of the excited states (which are not thermally acces-
sible) with the ground state in presence of an external magnetic field. Thus these higher energy levels
(i. e. E' ) kBD can contribute to XM through the 2nd order Zeeman effect but not through the 1st order
Zeeman effect.
• Temperature independent paramagnetism (TIP) from the 2nd order Zeeman effect: In presence
of an external magnetic field (H), the second order Zeeman effect allows the mixing of the excited states
ry
with the ground state but the excited states reside far above the ground state, i.e. the energy separation
is much larger than the thermal energy (kBD. Thus, the excited states are not thermally accessible.
ra
The external magnetic field (H) pushes some electron cloud into the excited state which has both
orbital and spin degeneracy. Thus the population density at the excited level does not depend on the
ib
thermal energy (which is too to small compared to the excitation energy) but on the applied magnetic
yl
field strength.
m
Zeeman Effect (cf. Appendix VIII)
he
Perturbation of energy levels by an external magnetic field is called the Zeeman effect. Energy
of a wave function 'Vi with respect to that of a reference level in presence of a magnetic field H
is given by: lc
E; = EP + E}H + EJIlfl + ...
ea
EP = energy of the unperturbed wave function 'Vi in absence of the field
E} = 1st order Zeeman coefficient
th
. E}I = 2nd order Zeeman coefficient, i.e. 2nd order Zeeman effect is characterised by the term
which depends on the square of the magnetic field strength.
e/
Magnetic moment of a molecule interacts with the magnetic field (H) and this interaction
t.m
lowers its energy. We can write:
- dE; I 2 II
f..l; =---=-E; - HE; - .
dH
e
fl; is the projection of the magnetic moment Ili along the field direction.
er
N N iI Ln.f..l.
XM = ----.A x average magnetic moment per molecule=~whereiI av = ~
H
H H L.Jn;
k
• MnOi or CrO~- (a'l-system) possessing the ground state which is nondegenerate both orbitally
lic
and in spin shows the weakly paramagnetic property because of the TIP. For Mn04 and CrOj-, these
are to be considered as the covalent moieties and in terms of MOT, all the electrons remain paired in
C
the MOs at the ground state. But the excited state is paramagnetic and the excited state contributes the
paramagnetism through the 2nd order effect.
• Energy levels both thermally accessible (i.e. E' « kBT) and thermally not accessible (i.e. E'»
kBT): Under the situation, both the 1st order and 2 nd order Zeeman effect will contribute to XM and
combination of these two sources lead to the Langevin-Curie equation:
C
+ NAu
T
~
~
Contribution of 2nd order
Contribution of 1st Zeeman effect.
order Zeeman effect
Considering both the Zeeman effects to contribute, Van-Vleck derived an equation of magnetic
susceptibility and the equation is known as Van-Vleck Equation (cf Appendix-VIllE) which can be
applied in different cases like multiplet width» kBT, « kBT and ~ kBT. This approach leads to the same
results (cf Appendix-VIllE).
8.15 QUENCHING OF ORBITAL CONTRIBUTION TO MAGNETIC MOMENT BY
ry
CRYSTAL FIELD
In the free atoms or ions in the gaseous phase, orbital contribution arises but in a chemical environment,
ra
the behaviour is totally different.
ib
For a free electron (s =±' L = 0, J = ±), g becomes 2 from the following equation.
yl
m
=1+ J(J+l)+S(S+I)-L(L+l)
g 2J(J + I)
he
For the free halogen atoms (ns 2np 7) in the gaseous phase, in the ground state
( 2 P3/2' L = 1, S = ±' J =
lc
%). according to the above equation, g becomes 4/3. These predictions are
ea
experimentally verified. But in a compound, for the electrons, the g-value depends on the chemical
environment.
th
If the orbital motion makes its full contribution to the magnetic moment, then it will lead to the
following relation in the cases where Land S do not couple effectively, i.e. they contribute independently.
e/
flS+L =J4S(S+I)+L(L+I) B.M.

t.m
But, in reality, the orbital contribuLlon is fully or partially quenched depending on the situation.
A. Possibility of quenching of orbital contribution: To understand the origin of quenching of orbital
contribution, we shall discuss the fate of d-orbital electrons in different crystal fields.
e
An electron will produce an orbital moment around a particular axis, if it is possible to trans-
form the orbital (which carries the electron) into an equivalent degenerate orbital around the axis.
er
This pictorial concept describes as if the electron is rotating about the axis. The d x 2 -y 2 orbital can
H
be converted into the dxy orbital through the rotation by 45° around the z-axis. Similarly: a rotation by
90° around the z-axis, converts the dxz orbital into the d.vz orbital. Rotation of the d xy orbital around the
k
x or y axis converts by 90° into the dxz or dvz orbital respectively. In the free species (or under the
lic
spherical field), all the five d-orbitals are degenerate and consequently the orbital moment exists. Thus
to have the orbital contribution to the magnetic moment, the following conditions must be satisfied.
C
(i) Condition of degeneracy: The concerned orbitals which are mutually transformable through the
symmetry operation must be degenerate.
(ii) Condition of mutual transformability through the symmetry rotation: The orbitals must be
mutually transformable by rotation about some axis.
It is illustrated for the d-orbitals.
d xy ( ) d x2 _y2 ; d xz ~ d yz ;
(Rotation by 45° around the z-axis) (Rotation by 90° around the z-axis)
dxy~dxz; dxy~dyZ;
(Rotation by 90° around the x-axis) (Rotation by 90° around the y-axis).
Thus it is evident that the mutually transformable (by rotation) d-orbitals are present in the t 2(g) set
of tetrahedral and octahedral crystal field. The d X2 _ y2 and d Z2 orbitals to constitute the e(g) set are not
mutually transformable because of their different shapes. Thus, the t 2(g) set can make an orbital
contribution but the e(g) set fails to make any orbital contribution.
(iii) Condition of spin: The orbitals must not contain the electrons of similar spin.
ry
B. Quenching of orbital moment in the octahedral and tetrahedral geometries: In the octahedral
crystal field, the d-orbitals are split into two groups:
ra
12g (dxy, d yZ ' dxz ) and eg (dx'-i' d Z2 )
ib
Thus, in an octahedral crystal field, the mutally transformable dxy. and dx2 _y2 orbitals are now
yl
nondegenerate (i.e. are of different energies). Consequently, orbital contribution from these orbitals is
m
quenched. The mutually transformable orbitals like dyz and dxz orbitals (90 0 rotation around the z-axis);
dxy and d yz orbitals (90 0 rotation around the y-axis); dxy and dxz orbitals (90 0 rotation around the x-axis)
he
are still degenerate and they can contribute to the orbital magnetic moment. Thus the orbital contribu-
tion from the t2g set is not fully quenched. A similar situation arises in the tetrahedral geometries when
the d-orbitals are split into two sets: lc
-' dzx) and e(dx 2_ y 2, d Z 2).
ea
t2 (dxv. ' d,.z'
The d x2 _ y2 and d Z2 orbitals of the e set are not mutually transformable by rotation. Thus, there is
th
no orbital contribution from the e set but the orbital contribution from the orbitals of t2 set is not
fully quenched, if the other conditions of orbital contribution are satisfied.
e/
Thus for the octahedral and tetrahedral crystal field, there is no orbital contribution from the eg
t.m
and e set (respectively) but the t 2g and t 2 set can make the orbital contribution if the third condition
of spin is satisfied. The third condition is illustrated below.
In the octahedral field, the ~g configuration fails to make any orbital contribution. Here the two
conditions, i.e. degeneracy and transforrilability are satisfied but on rotation, the dxz orbital converts
e
into the dyZ orbital which is already occupied by an electron of the same spin. Similarly, transformation
er
of the dxy orbital into the dxz orbital (rotation around the x-axis) or the dyz orbital into the dxy orbital
(rotation around the y-axis) leads to the same spin as that in the starting orbital. Because of the same
H
ground, the t2~ configuration cannot make any orbital contribution.

Thus in the octahedral and tetrahedral complexes, the following configurations can contribute to the
k
orbital magnetic moment.

lic
oh·. tIt 2 t 4 t 5 i e t x (x = 1 2 4 5) }
2g' 2g' 2g' 2g' • • 2g '" Ground state T -term (making an orbital contribution)
Td : t1, ti, t1, ti, i.e. t2 (x = 1,2,4,5)
C
For the above electronic configurations, all the three conditions for making an orbital contribution
are satisfied.
Here it is important to mention that the above configurations (which can make the orbital contribution)
experience the J.T. distortion which can lift the degeneracy. This distortion splits the three d-orbitals
(dxy', dyZ and dzx) into two groups - one group consists of the dxz and dyz orbitals while the other group
consists of the dxy orbital alone.
t~g or t~ dis~~~~on) (d xy) and (d yz ' dxz)

(x=1,2,4,5)
Thus even after Jahn-Teller splitting, the mutually transformable dxz and dyz orbitals remain
degenerate. Moreover, in general, the splitting in the t2 level is of so low magnitude that these three
orbitals may be practically considered as the degenerate orbitals.
Orbital Contribution: Octahedral vs. Square planar

The limiting situation of z-out distortion in an octahedral complex leads to the square planar
ry
geometry. Thus, degeneracy among the d.\)" d y: and d:,t orbitals is partially destroyed in a square
ra
planar complex and they are split into two groups: (dx.J and (dy:, d:,.'). The triply degenerate
group (d xy , d yz , d zx ) can make an orbital contribution better than the doubly degenerate (d yz ,
ib
d zx ) group. Thus the possibility of orbital contribution in the square planar complex is reduced
more compared to that in the octahedral complex. In general, in the low symmetry complexes
yl
(a crystal field effect), the orbital contribution is quenched more.
m
In Table 8.15.1, the cases of octahedral and tetrahedral systems where the orbital contribution exists
he
are given. It is evident that the ground states having the A and E terms cannot produce any orbital
contribution while the T-term can produce the contribution.
lc
Orbital Contribution to the Magnetic Moment
ea
• From the ground T-state (cf. Sec. 8.15)
• From the excited T-state through mixing with the ground state via spin-orbit coupling (cf.
th
Sec. 8.16)
• Contribution from the excited T-state via spin-orbit coupling may be positive or negative
e/
depending on the sign of spin-orbit coupling constant.

t.m
Table 8.15.1 Quenching of orbital contribution in the octahedral and tetrahedral complexes
Electronic Configuration Orbital Contribution
e
°h-system To-system °h-system To-system

(high-spin)
er
ti.~eT2~) el eE) Yes No

H
t~g CTI~) e 2 CA 2) Yes No

t2~ (4A2~) e 2ti (4T() No Yes
k
t2~ e,~ (5 E g) e 2ti CT2) No Yes

lic
ti: e~ (6A Ig) e 2tj,1 (6A I) No No

t2~ e,~ CT2~) eJti CE) Yes No
C
t2~ e; (4TI~) e4 ti (4A 2 ) Yes No

t2~ e,; CA 2g ) e4tf CT ) 1 No Yes
e1
t2~ eE~) e4 ti eT2) No Yes
°h-system
(low-spin)
t2~ CTI~) Yes
t:z~ e T2g) Yes
t2~ eA 1) No
t2~ e,~ eEg) No
c. Possibility of· orbital contribution in the square planar complexes and square pyramidal
complexes (cf. Secs. 8.24.7-8 and 8.25): The tetragonal elongation in the octahedral geometry pro-
duces the square planar geometry and square pyramidal geometry (cf. Fig. 8.15.1)
ry
ra
- - - a 1g (d Z 2)
======= e (d d yz)
ib
g XZI
(C 4) (C 4)
yl
Square planar Square pyramid Square pyramid
m
(cf. Fig. 3.5.6.1 (cf. Fig. 3.5.7.1) (cf. Sec. 8.25.1
Sec. 8.25.2) Fig. 8.24.5.3)
he
(a) (b) (c)
Fig. 8.15.1 z-out distortion in an octahedral geometry leads to (a) square planar geometry (a limiting situation of
lc
z-out distortion); (b) square pyramidal geometry (a consequence of z-out distortion also); (c) Square pyramidal geom-
etry when the metal centre lying above the basal plane (cf. Fig. 8.24.5.3) and in presence of good n-bonding ligands in
ea
the basal plane (e-f Sec. 8.25.1).
• Square planar geometry (cf. Sec. 8.24.7,8; 8.25.1): It is evident that the eR set (consisting of the
th
dx: and d\,: orbitals which can be mutually converted into one another by rotation of 90° about the z-axis)
can make the orbital contribution for the e} and ei configurations. Let us illustrate for the square planar
e/
complexes of Co(ll) (d?) having the electronic configuration (ground state): ei ali
big. It should not
have any orbital contribution. The magnetic moment should be close to the J.lspin value 1.83 B.M. due
t.m
to the one unpaired electron. But many square planar complexes of Co(ll) record the magnetic moment
much higher than 1.83 B.M.
[Co(salen)] (J.lobs= 2.25 B.M.), [Co(bigH)2]S04 (J.lobs = 2.70 B.M.).
e
Though the ground state is not capable of making any orbital contribution, the excited state, i. e.
eiai/J~g can make an orbital contribution from the ei configuration. Thus mixing of the excited state
er
with the ground state through spin-orbit coupling can enhance the magnetic moment to some extent.
H
But, this factor is not alone sufficient to explain the so high magnetic moment. Probably some other
factors are also responsible.
k
• Square pyramidal geometry (cf. Secs. 8.24.7,8; 8.25.1): The rationalisation of magnetic mo-
lic
ment of the square pyramidal complexes of Co(ll) is also difficult as in the case of its square planar
complexes.
[Co{Me2As(CH2)2As(Me)(CH2hAsMe2}12], J.leff = 2.36 B.M., 300 K
C
The ground state electronic configuration is:

e4bial i.e. (dxz ' d vz )4 (dx)l (dZ2 f
There is only one unpaired electron contributing J.lspin = 1.73 B.M. (cf. J.lobs =2.36 B.M.). The excited
state e3b} arcan make an orbital contribution through the mixing with the ground state via spin-orbit
coupling but this contribution is not sufficient to explain the so high magnetic moment.
Surprisingly, the magnetic moment of Ni(lll) (d?) complexes of square pyramidal geometry does not
show any such anomaly.
[NiBr3(PMe3)2], J.leff = 1.8 B.M. 300 K.
The spin only value of e4b2al configuration is 1.73 B.M. which is very close to the experimentally
observed value (1.8 B.M.). Thus it contrasts the behaviour of the square pyramidal complexes of Co(II).
To explain the anomalous magnetic moments of the square planar and square pyramidal
complexes of Co(II), possibilities of the contribution of intermediate spin and spin admixed states
may be considered (cf Sec. 8.25).
D. Conclusion: Orbital contribution from the ground state exists in the octahedral complexes of
ry
Ti(III) (d 1), V(III) (d 2 ), low-spin Mn(III) (d 4 ), low-spin Fe(lll) Cd 5 ), high-spin Fe(ll) (d 6 ), high-spin
Co(III) (d 6 ), high-spin Co(ll) (d?) etc. In such octahedral complexes, the observed magnetic moment
ra
should be higher than the J..lspin-only value. The square planar and square pyramidal complexes may also
ib
have the orbital contribution depending on the electronic configuration.
The terahedral complexes of d 3 , d 4 configurations and Ni(II) (d 8 ), Cu(II) (d 9 ) are expected to enjoy
yl
the orbital contribution.
m
8.16 MIXING OF THE GROUND STATE WITH THE EXCITED STATE VIA SPIN-ORBIT
COUPLING: ORBITAL CONTRIBUTION FROM THE EXCITED STATE THROUGH
he
SPIN-ORBIT COUPLING
There are cases where the electronic configuration of the ground states (i. e. A and E terms) cannot
lc
satisfy the required conditions for an orbital contribution, but their excited states (that can be repre-
ea
sented by T term) are suitable for making an orbital contribution. In such cases, mixing between the
excited and ground state through the spin-orbit coupling can introduce some orbital contribution to the
total magnetic moment.
th
Actually, through the spin-orbit coupling, some T-character (which can make an orbital contribution)
of the excited state is introduced into the nonmagnetic (in the sense of orbital contribution) ground A
e/
or E states. To carry out a such mixing through the spin-orbit coupling, the following conditions are to
t.m
be satisfied.
(i) Condition of unpaired electrons: Both the ground and excited states must be paramagnetic with
respect to the unpaired electrons.
(ii) Condition of spin multiplicity: The number of unpaired electrons in the two states must be
e
identical, i.e. spin-multiplicity (2S + I) of the two states to be mixed through spin-orbit coupling must
er
be the same. The above two required conditions can be stated as follows:
The T-term can make an orbital contribution. Thus, if there is an excited T-state having the same
H
spin multiplicity as with the ground state and if it can mix with the ground state through the spin-
orbit coupling, then an orbital contribution from the excited state can occur.
k
If the above conditions are satisfied, the effective magnetic moment (J..leff) is given by:
lic
Il eff = Ilspin-only (1- l:q)B.M.

C
E(T2 ) - E(A 2 ) = IODq; E (T2 ) - E(E) = IODq

i i i i
1st excited Ground 1st excited Ground
state state state state
where a = 2 (for the E(g) ground state), 4 (for theA 2(g) ground state); IODq gives the separation of energy
between the ground and first excited state, A is the spin-orbit coupling constant. A is a positive quantity
for the first transition metal ions having the electronic configurations d 1 to d 4 (i.e. less than half-tilled)
and it is negative for those having the electronic configurations d 6 to d 9 (i.e. more than half-filled).
Thus we can conclude:
• for the high-spin d 6 to d 9 configurations

Ileff ) Ils pin-only
l 4
• fleff ( J,tspin-only for the high-spin d to d configurations.
For the higher values of 1ODq, the mixing effect becomes less significant, i. e. orbital contribution
from the excited state through the spin-orbit coupling is less important for the stronger field ligands.
10Dq value in an octahedral complex is generally much higher than that in a tetrahedral complex. Thus,
the spin-orbit coupling contribution is more important in a tetrahedral complex compared to that in
ry
an octahedral complex.
ra
Similarly, in the low-spin octahedral complexes, the 10Dq value is larger than that in the high-spin
complexes. Thus, the spin-orbit coupling interaction in a low-spin complex is relatively small.
ib
Table 8.16.1 Spin-orbit coupling constants (A) and the values of aA for some 1st transition metal ions.
yl
(cf. Table 8.13.1)
m
Metal ion and Complex Ground state
free ion term Symmetry level in the complex
he
V 4+(3d l ), 2D 3/2 Td 250 500
Cr3+(3d3 ), 4F3/2
Cr2+(3tr), 5Do
°h0h (h.s.) lc 92
58
368
116
ea
Fe 2+(3lJ6), 5D4 Td -100 -200
Co 2+(3cf'), 4F 912 Td -172 -688
th
C o2+(3cf'), 4F9/2 0h (l.s.) -515 -1030

Ni 2+(3tJ8), 3F 4
°h -315 -1260
e/
Cu 2+(3JJ), 2D512
°h -830 -1660
t.m
Temperature dependence of spin-orbit coupling contribution for the A and Eterms

It has been already pointed out that at the ground state, the A and E terms cannot make any orbital
e
contribution. But if there is any suitable excited T-state then it can introduce the orbital contribution
via spin-orbit coupling. The energy difference between the ground and excited state is usually in
er
the order of 10,000 cm- l which is much higher than the thermal energy kBT (-200 cm- l at 300 K).
H
Consequently, this spin-orbit coupling contribution does not significantly depend on the
temperature.
k
lic
(A) Limitation of the Eqn. Ileff =(1- l:q }sPin-onIY:

C
The above equation is applicable only for the systems having the A and E ground states. Thus it is
only applicable for the following systems:
0h Complexes: d 3 , tf (h.s.), eP (l.s.) cJ8, tf
Td Complexes: d l , tP, cJ6, d'
For the systems having the T. or T~ ground state, the above equation is not applicable. Spin-
orbit coupling can split the T-terms (cf. Figs. 7.7.4.2, and Sec. 8.20) and the separation energy is
comparable to kBT. Thus, the population density of the different states developed through the spin-
orbit coupling splitting of the T-term is thermally controlled and the ma~netic property depends on
temperature.
It may be noted that the A and E terms do not undergo splitting through the spin-orbit coupling and
the magnetic properties are more or less insensitive to temperature (cf Sec. 8.20).
(B) Magnetic property: A and E terms vs. T-term (cf. Sec. 8.20):
• Ground state of T-term can enjoy the orbital contribution and very often the f.!eff) f.!spin condition
is maintained. For the A and E terms, the orbital contribution is absent at the ground state but there may
be a spin-orbit coupling contribution from the excited T-state. This spin-orbit coupling interaction
ry
makes f.!eff ) f.!spin or f.!eff < f.!spin depending on the condition.
For the high spin cf- 9 systems (A = -ve) and it makes f.!eff ) f.!spin and f.!eff < f.!spin for the d l - 4 systems
ra
(A = +ve) .
• The magnetic properties of the T-term are highly dependent on temperature (cf Sec. 8.20) while
ib
the magnetic properties of the A and E terms are more or less insensitive to the temperature variation.
yl
(C) Orbital contribution from the excited state in square planar complexes: Possibility of orbital
contribution from the excited state of Co(II)-square planar complex has been discussed in the previous
m
section (cf Sec. 8.15).
Note: We have already mentioned that the First order Zeeman Effect leads to:
he
Jleff = gJ](] + I) B.M.
Under the condition L = 0, Le. ] = S, it leads to: lc
ea
Jlspin-only = gJS(S + 1) B.M. = 2JS(S + I) B.M.
When there is a mixing of the excited state term with the ground state term through spin-orbit coupling,
th
the g-factor, instead of 2, is changed as follows:
g=2(1-~J
e/
10Dq
t.m
i.e. Jleff =2(1-~JJS(S+I)

10Dq
B.M.
e
=(I-~JJ4S(S +1) B.M.

er
IODq
H
= (1- I~~q JllsPin-onl Y

k
2
(I J-
UA
?
lic
_ N A Jl eff _ N A 2
XM(eff) - 3k T - 3k T - IODq Jlspin-only
B B
_(I
C
u'A J2 NA 2
- - 10Dq 3k T Jlspin-only
B
~ (1- I~~q JXM(SPin-OnlY)

i.e. XM(ejf) ~ (I -I~~~ JXM(SPin-OnlY)
U =4for A 2(g) term, U =2for term and =0 for
E(g) U A1(g) term (i.e. no mixing through this mechanism).
(D) Determination of spin-orbit coupling constant from the magnetic data: It has been already
pointed out that mixing of the ground state with the excited state (capable of making an orbital
contribution) of the same spin-multiplicity via spin-orbit couping changes the splitting factor ge (= 2,
for L =0) as follows:
(1-~J
ry
-
g-ge 10Dq
ra
i.e. g= 2 ( 1- 1~~q]. for the A 2 (g) ground state.
ib
yl
and g =2 (1 -~J, for the ground state.
m
E(g)
10Dq
he
The g value can be obtained from the ESR measurement of the complex under consideration. The,
10Dq value can be obtained from the electronic spectra. By using the experimental values of g and
10Dq, the spin-orbit coupling constant (A) can be calculated from the above relations.
lc
From the measurement of J.leff' the spin-orbit coupling constant can also be obtained.
ea
~eff = (1- l~~q J~sPin-OnlY' (For the A 2(g) ground state)
th
~eff = (1- l~~q J~sPin-OnlY'

e/
(For the E(g) ground state)

t.m
By using the experimental values of J.leff, 10Dq and the theoretical value of J.lspin-only, the spin-orbit
coupling constant (A) can be calculated by using the above equations.
By using the relation, A = ± (j2S, the single electron spin-orbit coupling constant ~ can be
e
obtained (cf. Table 8.13.1).

er
Here it may be mentioned that the magnitude of A (in complex) is reduced (compared to that of the
free ion value) due to the nephelauxetic effect causing an effective increase in orbit radius (cf. Sec.
H
8.13). This is why, the following ratio is less than unity.

k
A(complex)
( . ) < 1, (cf Table 8.13.3)
lic
A free Ion
C
The ratio less than unity is an indication of covalence in the metal ligand bond, i. e. nephelauxetic
effect.
8.17 MIXING OFTHE EXCITED TERMS WITH THE GROUND STATE TERM THROUGH
THE SECOND ORDER ZEEMAN EFFECT (ct. Sec. 8.22)
It has been already mentioned that the spin-orbit coupling can allow the mixing of the ground state term
with the excited terms having the same spin multiplicity. The 2nd order Zeeman effect can also allow
the mixing of the higher states with the ground state of the same spin multiplicity under the influence
of an external magnetic field.
(A) Conditions for the 2nd order Zeeman effect: Mixing of the ground state with the excited state
via the 2nd order Zeeman effect can occur under the following conditions:
(i) The ground state and excited states to be mixed must have the same spin multiplicity.
(ii) The excited state must have both the orbital and spin degeneracy.
(iii) The 2nd order effect exists only in presence of an external field (H) that pushes some electron
cloud into the excited state.
ry
(iv) The i-values between these interacting states must not differ by more than unity.
(v) The second order effect is independent of temperature. The energy separation between the ground
ra
and excited state is much higher than the thermal energy kBT. Consequently, the excited is not
thermally populated and the 2nd order effect becomes independent of temperature. But, if the
ib
excited state is not far away from the ground state (as in the case of Sm III and EU III ) then the XM
yl
(2 nd order) becomes dependent on temperature. This aspect has been discussed in Sec. 8.22. Thus
XM (2 nd order) leads to TIP only when the energy difference between the excited and ground
m
state is much larger than the thermal energy (kBT).
(vi) If the ground state is diamagnetic (i.e. S = 0), then mixing of an excited state (capable of making
he
an orbital contribution as in the case of low-spin octahedral complexes of COllI) with the ground
state via spin-orbit coupling cannot produce any paramagnetic susceptibility. But in such cases,
lc
mixing of the ground state with the excited state under the influence of a magnetic field (i.e. 2nd
order Zeeman effect) can generate a paramagnetism.
ea
Participation of the excited state to induce the paramagnetism:
th
Spin-orbit coupling effect VB. 2nd Zeeman effect

e/
For both the mechanisms, the interacting states, i. e. ground state and excited state must have the
same spin multiplicity. For the spin-orbit coupling mechanism, the ground state must not be
t.m
diamagnetic itself but the second order effect can occur even for the diamagnetic ground state
provided the excited state is paramagnetic (i.e. capable for making an orbital contribution). This
is why, the low spin Co(III) complexes (~g, lA 1g ) do not experience the paramagnetism from the
spin-orbit coupling pathway but they can enjoy the small paramagnetism from the 2nd order Zeeman
e
e
effect through the interaction with the excited state T 1g ).
er
(B) 2nd order Zeeman effect and paramagnetism in Mn04- and CrOj- (cJ. Sec. 8.22.2 for
H
details): MnOi (do) or CrOl- (do) possessing the ground state which is nondegenerate (both orbitally
and in spin) (i.e. singlet both orbitally and in spin) shows a small paramagnetism due to the 2nd order
k
Zeeman effect (i.e. TIP). In terms of the ionic model, i.e. CFT, the dO system (L = 0, S = 0), cannot
lic
experience both the Ist order and 2nd order Zeeman effect to induce the paramagnetism. But, if the
species Mn04 and CrOl- are treated as the covalent species, then in terms of MOT, the ground state is
C
diamagnetic but the excited state is paramagnetic. Thus the species can enjoy the 2nd order effect, i.e.
TIP.
(C) 2nd order Zeeman effect and TIP for the A2 and E ground state: The second order Zeeman
effect produces the temperature independent paramagnetism (TIP). This aspect will be discussed in
detail later. Here we shall only consider the result.
• Low-spin Co(III) complexes: For the low-spin octahedral complexes of Co(III) (i.e. ~g), the
ground state term lA 19 (diamagnetic, no unpaired electron) undergoes mixing with the excited states
(i. e. I T 1g , I T2g ) having the orbital contribution through the 2nd order Zeeman effect. It may be noted
that the mixing of these excited states through the spin-orbit coupling is not possible because· the
S
diamagnetic ground state (lA 1g ) is associated with = O. TIP for the low-spin octahedral complexes of
Co(lll) for mixing of the excited state IT lg with the ground state lA lg is given by:
2
8N A B
XM(TIP) = 10Dq
The 10Dq value can be estimated from the lA lg ~ ITlg transition energy (see Chapter 7).
ry
• High-spin d5 system: For the high-spin d5-octahedral system, the ground state is 6A 19 which does
ra
not have any orbital angular momentum (L = 0). Here there is no excited term having the same spin
multiplicity as in 6A 19. This is why, the ground state 6A 19 cannot interact with any excited state either
ib
via the spin-orbit coupling or via the 2nd order Zeeman effect. In such cases, the observed magnetic
moment (-5.97 B.M.) is very close to the f.lspin-only value.
yl
• For the A 2 ground state: XM(TIP) for the A 2 ground state (e.g. 4A 2g for CrIll, ad3 system, the next
m
excited state is 4T2g ),
he
2 2
8NAB 8NAB eh
XM(TIP),A 2 = E(T )-E(A
2 2
) = lODq ,~= 41tme c
It indicates that is in the order of (10 - 100) x 10-6 (CGS unit)
XM(TIP)
lc
ea
• XM (Total) for the A 2 ground state: The total magnetic susceptibility due to both the I st order
Zeeman effect (including the spin-orbit coupling) and 2nd order Zeeman effect for the A 2 state (e.g.
th
octahedral ~, ff'; tetrahedral d') is given by:
J B2
e/
8A 8N A
X~(TolaI) =,( 1-wvq ,XM(sPin-onl Y), + ~
t.m
1st order Zeeman effect 2 nd order Zeeman effect
= (1- -~J N AIl;Pin_only~2 + 8NA~2 • . = ~4S(S + 1) B.M.

e
lODq 3k T lODq , Ilspm-only

B
er
• XM (Total) for the A 2 ground state as in the octahedral Ni(II) complexes: For the 3A 2g ground
state as in the octahedral Ni(II)-complexes (S = I, 2S + I = 3) with the first excited state 3T2g (i.e.
H
energy difference between the ground state and excited state = IODq):
k
(1- l~~q
lic
We can write: Il eff = )llsPin-onI Y ; (ignoring the 2nd order effect)

C
= (1-~)J4S(S + I) ~
10Dq
=(I-~Jv18
10Dq
B, (S=I)
= N AtJA2 Jlspin-only
2 ~
1-)
( 2 = 1-) 2
( ~
3k T 10Dq XM(spin-only) 10Dq
B
3 A2 = NA~2 8(1-~)+ 8NA~2 = (1-~)+ 8NA~2

XM(TotaI) 3k T 10Dq 10Dq XM(spin-only) 10Dq 10Dq
ry
B
• For the E(g) state as in the systems like octahedral Cu(II) (tfJ) complexes (ground state 2Eg , 1st
ra
excited state 2T2g ; energy separation between these states = 1ODq), Cr(II) (d4 ) octahedral complexes
and tetrahedral complexes of d 1, cJ6 systems, XM(TIP) is given by:
ib
2
4N A B
yl
10Dq
m
2
=(1-~) 4N A B
he
E
XM(TotaI) 10Dq XM(spin-only) +
10Dq
, J
'--v---'
2nd order Zeeman effect
1st order Zeeman effect
E-ground state occurs for the high-spin octahedral d4 , low-spin octahedral d7 and
lc cP configurations. For
ea
the cJ4 system, the ground state is 5E g (S = 2) and the 1st excited state is 5T2g ; and XM(total) is given by:
= (1-~))4S(S + 1) B=(1-~)J24B
th
Jleff
10Dq 10Dq
e/
t.m
i.e.
e
er
NA~2 X24(1-~)+ 4NA~2

H
5£ _
XM(Total) - 3k T lODq lODq
B
\ J '--v---'
k
1st order Zeeman effect 2nd order

Zeeman effect
lic
Note: The XM(TIP), a consequence of 2nd order Zeeman effect, i. e. mixing of the ground state with the
excited state (capable of making an orbital contribution) under the influence of an external magnetic
C
field (H), is relatively small compared to the XM arising from the 1st order Zeeman effect. Thus, XM(TIP)
becomes accountable when XM(spin-only) is absent. It happens so for the complexes like low-spin Co(III)
complexes (t2~).
(D) Orbital reduction factor (k) in expressing the 1st order and 2nd order Zeeman paramagnetic
susceptibilities: Covalence in the metal-ligand bond leads to an electron delocalisation (i.e. nephelauxetic
effect). Because of this electron delocalisation, the orbital angular momentum is reduced by a factor,
called delocalisation factor denoted by k which is commonly known as orbital reduction factor.
Consideration of this factor, changes the 1st order and 2nd order Zeeman paramagnetic susceptibilities
as follows:
aAk2
g = ge ( 1- lODq , ge
J = 2.0
4k2A,
= ( 1- lODq
J
ry
lleff llspin-only'
8k2N ~2
ra
XM(TIP) or XM(2nd order) -- A
10Dq For A(g) term.
ib
8k2A, ] 8k N ~2
2
- 1--- +
yl
A
XM(Total) - XM(spin-only) [ 10Dq 10Dq
m
he
lleff
2k2A,
= ( 1- lODq
J
llspin-only'
XM(TIP) or XM(2nd order) --

4k2N ~2
lc
ea
A
10Dq For E(g) term.
4k2A, ] 4k N ~2
2
th
- 1--- + A
XM(total) - XM(spin-only) [ 10Dq 10Dq
e/
XM(Total) is an experimental quantity and XM(spin-only) can be theoretically calculated; A can be obtained
t.m
from the ESR data. Thus, by using the above equations of XM(total)' k can be calculated. The value of k
less than unity suggests the covalence in the metal-ligand bond. The orbital reduction factor will be
discussed at a greater length later.
e
8.18 MAGNETIC PROPERTIES OFTHE COMPLEXES OF FIRST TRANSITION

er
METAL IONS
H
8.18.1 General Magnetic Behaviour of the Complexes of 3d-Metal Ions

The characteristic observations are summarised below:
k
(a) Closeness between J..ts and J..I.obs: The plot of J.ls vs. d n (0 - 10) produces a single-humped curve
lic
having the maximum at d 5 (jor the high-spin 0h and T d complexes). For the d l - 4 systems (h.s. 0h and
Td ), J.lobs nicely matches with J.ls but, the (]6 - 9 systems (h.s. 0h and Td ) deviate significantly from J.ls.
C
This is specially noted for the Co(ll) and Ni(ll) complexes.

(b) Orbital contribution quenched significantly: The 3d-orbitals are exposed towards the ligand
environment and the necessary conditions for an orbital contribution are very often lifted away by the
crystal field. It leads to L = O. It indicates that the conditions for J.lJ and J.lL+S are not satisfied. It makes
J.lobs close to J.ls.
(c) fJ.obs) J..ts for the T-ground state making a partial orbital contribution: The orbital contribution
is fully quenched for the A and E ground state terms while for the ground T-state, the orbital contribu-
tion is only partially quenched. In other words, for the T-ground state, the orbital contribution occurs
partially and the observed magnetic moment becomes higher than the J.!spin-only value.
Table 8.18.1.1 Magnetic properties of the first transition series metal ions in octahedral (high-spin states)
and tetrahedral complexes.
Ions Free ion Ground state Ground state J.Ls J.LL+S J.LJ Jlobs
Ground state term term in a weak term in a (H.M.) (B.M.) (B.M.) (H.M.)
octahedral tetrahedral
S L Term field field
ry
3d' (Ti 3+, ~+) 1/2 2 2D 3/2 2T2~ 2E 1.73 3.0 1.55 1.6-1.8
ra
3~ (y3+, Cc4+) 3 3F2 3T,~ 3A 2 2.83 4.47 1:63 2.7-2.9
ib
3d3(Cr 3+, Mn4+) 3/2 3 4F3/2 4A 2g 4T, 3.87 5.20 0.77 3.7-3.9
yl
3tJ4(Cr2+, Mn 3+) 2 2 5Do 5E~ 5T2 4.90 5.48 0 4.8-5.3
3tF(Mn 2+, Fe 3+) 5/2 6S5/2 6A, 5.9-6.0
m
0 6A'g 5.92 5.92 5.92
3lf(Fe 2+, Co 3+) 2 2 5D4 5T2g 5E 4.90 5.48 6.70 5.1-5.6
he
3d' (C 0 2+, Ni 3+) 3/2 3 4F9/ 2 4T'g 4A 2 3.87 5.20 6.64 4.2-5.2
3lf8(Ni 2+, Cu 3+) 3F4 3A2~ 3T,
3tfJ(Cu 2+) 1/2

3
2 2D 5/2 2E~
lc
2T2
2.83
1.73
4.47
3.00
5.59
3.55
2.8-4.0
1.8-2.2
ea
Note: • Splitting of Russel-Saunders terms (S, P, D, F, G) in an octahedral field.
th
S ~ A'g; p ~ T'g; D ~ T2g + E~; F ~ A 2g + T2g + T,g; G ~ A'g + Eg + T,~ + T2g

e/
• Ground state term in the crystal field can be easily obtained from Orgel diagram (cf. Chapter 7).
t.m
6.0
e
er
5.0
H
4.0
~s
k
"',lJ
lic
ai 3.0
.£ /'(
:r /' (a single humped "
"\l}
C
2.0 /// symmetrical curve)
I ,
I ,
1.0 I
I ,
,
I ,
I ,
I ,
I
Fig. 8.18.1.1 Qualitative representation of f.ls and f.lobs values for the high-spin 0h and Td complexes of (f1 systems of
1st transition series.
Table 8.18.1.2 Magnetic moment of some octahedral complexes of 1st transition series
Compound 3dn No. of unpaired Ground state Jls Jlobs

electrons (H.M.) (H.M.)
High-spin complexes
K 3[TiF6] 3d\ 1 2T
2g 1.73 1.70
ry
[VO(Qh] 3d\ 1 2T
2g 1.73 1.70
3~
ra
NH 4V(S04h·12H 2O 2 3T\g 2.83 2.80
[V(acac)3] 3d2 2 3T\g 2.83 2.80
ib
3 3.85
KCr(S04h·12H 2O 3d 3 4A
2g 3.87
[Cr(bigH)3]CI 3 3d3 3 4A 3.87 3.85
yl
2g
Cr(S04) ·6H 2O 3d4 4 5E

g 4.90 4.82
m
[Mn(acach] 3d4 4 5Eg 4.90 4.86
Na[Mn(salgIYh] 3d4
4 5Eg 4.90 4.80
he
Na3[FeF6] 3d5 5 6A\g 5.92 5.85
K2Mn(S04h·6H 2O 3d5 5 6A\g 5.92 5.90
KFe(S04h·12H 2O 3d5 5 lc 6A\g 5.92 5.90
ea
6 5.47
(NH4hFe(S04h·6H 2O 3d 4 5T
2g 4.90
[Co(OH 2)6]S04 3d? 3 4T\g 3.87 5.10
(NH 4hNi(S04h·6H 2O 3d8 2 3A 2.83 3.25
th
2g
[Ni(NH 3)6]CI 2 3d8 2 3A

2g 2.83 3.32
e/
K2Cu(S04)2· 6H20 3tP 1 2E

g 1.73 1.91
Low-spin complexes
t.m
K3[Mn(CN)6] 3d4 2 3T\g 2.83 3.50

K3 [Fe(CN)6] 3d5 1 2T
2g 1.73 2.25
5 2.20
K4[Mn(CN)6] ·3H 2O 3d 1 2T
2g 1.73
e
K4[Fe(CN)6] 3d6 0 \A\g 0 0.35

er
[Co(NH 3)6]C1 3 3d6 0 \A\g 0 0.45

K 2Ba[Co(N0 2)6] 3d? 1 2E
g 1.73 1.88
H
00
k
HQ stands for quinaldinic acid

lic
N C0 2 H
C
Table 8.18.1.3 Magnetic moments of some tetrahedral complexes of 1st transition metal ions
Compound 3dn No. of unpaired Ground state Jls !Jobs

electrons term (H.M.) (H.M.)
[VC14] 3d\ 1 2E(e\) 1.73 1.70

(Et4Nh[MnCI 4] 3d5
5 6A \ (e 2 t 23 ) 5.92 5.93
(Et4N)[FeCI 4] 3d5 5 6A \ (e 2 t 23 ) 5.92 5.92
(Contd.)
Table 8.18.1.3 contd.
(Et4 Nh[FeCI 4 ] 3cP 4 5£ (e 2 tz3) 4.90 5.40

Cs z[CoCI4 ] 3d' 3 4A z (e 4tz3) 3.87 4.70
(Et4Nh[NiCI4 ] 3tJ8 2 3T1 (e 2 tz4 ) 2.83 3.90
Cs z[CuCI4 ] 3lf 1 2Tz (e 4 tz5) 1.73 2.0
ry
Table 8.18.1.4 Magnetic moments of some complexes of 1st transition metal ions of other geometries
ra
Compound 3dn No. of unpaired Jls (H.M.) J.lobs (H.M.)
ib
electrons
[VO(acac )z] 3d l 1.73 1.70
yl
(Square pyramidal)
m
[Co(bigH)2] SO 4 3d' 1.73 2.50
(Square planar)
he
[Cu(bigHh]CI 2 3et 1.73 1.80
(Square planar)
d l (Square pyramidal): (dxy) 1 lc

d' (Square planar): (dxz ' dyz )4 (d Z2 )2 (dxy)l
ea
If (Square planar): (dxz ' dyz )4 (d Z2 )2 (d~v)z (dx2 -l )1
Energy order for square planar (D4h ): (dxz ' dyz ) ::::; (d Z2 ) <dX}, < d x2 _ l
th
Energy order for square pyramid (C4v ): (dxz ' dyz ) <dX}, < d Z2 < d x 2 -l (in absence of n-bonding); d.ry <(dxz' dyz ) < d i < d x 2 -l
(in presence ofn-bonding and the metal centre lying above the plane), (cf. Sec. 8.25.1, Figs. 8.15.1, 8.24.5.3).
e/
It explains the higher magnetic moment (i.e. fJ.obs ) JJ.spin-only) for the high-spin octahedral Co(ll)
i
t.m
(t2 ei, 4Ttg ground state), high-spin octahedral Fe(ll) (t~ e;, ST2g ), tetrahedral Ni(ll) (eSt?, 3Tt ),
tetrahedral Cu(ll) (e4t~, 2T2) complexes.
It is reasonable to expect that the octahedral complexes of d1(i.e. tl g , 2T2g ), cfl (Le. tig 3T1g ) and
tetrahedral complexes of d3 (e 2tJ, 4T1) and d4 (ei ti, 5T2) systems should record the higher magnetic
e
moment (i.e. J.lobs) J.lspin-only) because of the orbital contribution. But, in such cases J.lobs is very close to
er
J.lspin-only. It needs an explanation to be discussed in the next paragraph.

(d) Joint effect of the orbital contribution from the ground state and excited state through the
H
spin-orbit coupling: For the high-spin octahedral complexes and tetrahedral complexes:
J.lobs ::::; J.ls (for d l - 4 ), J.lobs = J.ls (~), J.lobs ) J.ls (tf - cP).
k
For the less than half-filled d-orbitals (i.e. dX , x = 1 - 4), the spin-orbit coupling constant (A) is
lic
positive. Thus, the orbital contribution from the excited state through spin-orbit coupling (if possible)
will make a negative contribution. This negative contribution from the excited state can off-set the
C
orbital contribution from the ground state in some cases. These two opposing contributions mutually
nulify to some extent. It makes J.lobs close to J.lspin-only. It is illustrated in Table 8.18.1.5 by taking some
examples.
For the high-spin 0h and Td complexes of dX(x = 6 - 9), J.lobs ) J.ls can be explained in the same way.
For such systems (A = -ve), the orbital contribution from both the ground and excited states (if
possible) work in the same direction to increase the magnetic moment.
It can make, J.lobs ) J.lspin-only.
Note: Prediction for the ground state T-term is not so straight-forward because the T-term undergoes
splitting due to spin-orbit coupling.
Table 8.18.1.5 Orbital contribution from the ground state and the spin-orbit coupling contribution for the
d l -4 systems.
Jl (in D.M.) Orbital Contribution from Remarks on

expectation
H.S.O h ground state excited state
and Td (JJ.obs) Jls (positive (via spin-orbit
contribution) coupling)
ry
(negative
contribution)
ra
y4+(d 1) 1.68-1.78 1.73 t2~ (Yes) fJ.obs ) fJ.s
ib
y3+(cP) 2.75-2.85 2.83 t2 i (Yes) t2~ e~ (Yes) fJ.obs::::: fJ.s
Cr3+(d3 ) °h t2~ i
t2 e~ (Yes)
yl
3.70-3.90 3.87 (No) fJ.obs < fJ.s
Cr2+(tf) 4.4-4.90 4.90 t2~ ei(No) i
t2 e~ (Yes) fJ.obs < fJ.s
m
d1 e 1 (No) eOti (Yes) fJ.obs < fJ.s
cP e 2 (No) e1tl (Yes)
he
fJ.obs < fJ.s
d3 Td e2ti (Yes) e1(J (Yes) fJ.obs::::: fJ.s
d 4
e 2t? (Yes) e1tl (No) fJ.obs ) fJ.s
lc
ea
(e) Deviation of Jlobs from Jls for the A 2 and E ground state terms: There is no orbital contribution
for the A and E ground state but in such cases, mixing of the excited state (capable of making an orbital
contribution) with the ground state via spin-orbit coupling can introduce some orbital contribution from
th
the excited state. But this contribution may make a positive contribution (i.e. J.lobs ) J.ls) or negative
contribution (i.e. J.lobs ( J.ls) depending on the sign of spin-orbit coupling constant ('A). It is evident from
e/
the following relations.

t.m
Il = (l-~Jf.l a=2fortheE ground state

eff 10 Dq s' a = 4 for the A2 ground state
If A = +ve (for d l - 4 systems), then J.leff ( J.ls
e
and if A = -ve (for cf-9 systems), then J.leff ) J.ls.

er
However, with the increase of lODq value, the spin-orbit coupling contribution decreases but it
increases with the increase of the value of spin-orbit coupling constant ('A).
H
Spin-orbit coupling contribution for the A and E ground state

k
l
d (Td and h.s. 0h): J.lobs (J.lspin-only, A = +ve.
-4
lic
J.lobs is expected to be slightly less than J.lspin-only due to the spin-orbit coupling effect but the orbital
contribution (if possible) from the ground state can oppose this spin-orbit coupling contribution
C
effect; it may lead to Jlobs =:: Ilspin.

tr-9 (Td and h.s. 0h): J.lobs ) J.lspin-only, A = -ve.
J.lobs is expected to be significantly larger than J.lspin-only due to both the spin-orbit coupling effect
and orbital contribution (if possible) effect from the ground state.
(0 Examples of complexes for which Jlobs :I: Jlspin: Let us illustrate the effect of spin-orbit coupling
and orbital contribution on the magnetic properties by taking some specific examples.
• Octahedral Ni(II) complexes (t2~ ei,
3A 2g ) do not have any orbital contribution from the ground
state but the excited states (t2~ e~, 3T2g ; t 2; ei,
3T1g ) can make an orbital contribution. The energy
difference between the 3A 2g and 1st excited state 3T2g is IODq. The second excited state (i.e. 3TIg ) is of
much higher energy. Mixing of the excited state (3T2g ) with the ground state via spin-orbit coupling
introduces the orbital contribution. Here A = -ve and it makes Jleff) Jlspin-only.
• Tetrahedral complexes of Co(II) (e 4ti, 4A 2 ) is unable to make any orbital contribution from its
ground state but its excited state (e 3t 24 , 4T2 ) can make an orbital contribution through the spin-orbit
coupling. The negative value of A makes, Jleff ) Jlspin-only.
ry
• High spin complexes of d3,4- systems: In the same way, the high-spin octahedral complexes of
Cr(III) (tlg , 4A 2g ), Mn(III) (t~~:, 5Eg ) can also bring about the spin-orbit coupling contribution but
ra
because of the positive value of A, the observed magnetic moment is expected to be slightly less than
ib
Jls (i. e. Jlobs ( Jls)·
• Tetrahedral complexes of d1-system: Let us illustrate for [VCI 4 ] (IODq ~ 8,000 cm- I ),
yl
A = 250 cm- I , a = 2 for the E-ground state of [VCI 4 ].
m
Jlspin-only = Jls = JI (1 + 2) B.M. = 1.73 B.M.
he
Jleff
2 x-250)
= ( 1- - - x 1.73 B.M. ~ 1.63 B.M.
8000
lc
This calculated value approximately matches with the experimental value 1.68 B.M. Thus, the spin-
ea
orbit coupling can make Jleff ( Jlspin-only.
• Octahedral low-spin complexes: For the d 4 . system (t 2;, 3T Ig ), cP system (t2~' 2T2g ), the required
conditions for the orbital contribution are satisfied and their observed magnetic moment is significantly
th
greater than Jlspin-only (i. e. Jlobs ) Jls). For the d7-system (t2~ e~), there is no orbital contribution from the
e/
ground state and Jlobs is close to Jleff.

• Low spin tfi-systems: For the cf-system (t2~' IA 19), there is no spin contribution and no orbital
t.m
contribution to the magnetic moment from the ground state. The small observed magnetic moment is
due to TIP (i.e. 2nd order Zeeman effect).
8.18.2 Comparison of the Magnetic Properties of Fe(II), Co(II), Ni(lI) and Cu(lI) Complexes
e
(A) Fe(II) octahedral and tetrahedral complexes:

er
Jlobs (B.M.) Jls (B.M.)

Octahedral (h.s.) complexes (t2;e,~, 5T2g ): 5.1-5.6 4.9
H
Octahedral (l.s.) complexes (t2~' IA Ig): -0.3 0

Tetrahedral complexes (e 3ti, 5E):
k
5.2-5.4 4.9
lic
• Octahedral (h.s.) complexes experience the orbital contribution in the ground state (i.e. Jlobs >
Jlspi~-OnlY) and the excited state (t2~ e~) cannot make any orbital contribution through the spin-orbit
C
coupling interaction.
• The tetrahedral complexes fail to earn any orbital contribution from the ground state but the
excited state (e 2 t1) is capable of making an orbital contribution through the spin-orbit coupling.
Here, A = -ve and it makes, Jleff > Jlspin
/leff =(l-l~~q)/lsPin-onlY' A=-ve. i.e. /leff >/lspin-ooly'
• The octahedral (l.s.) complexes of Fe(II) (t~ge~) experience only a small TIP. Here it is
given by:
Note: The spin state isomerism, i.e. low spin ~ high spin, in the octahedral complexes of Fe(II)
may lead to an anomalous magnetic behaviour (cf Secs. 8.24-25).
ry
(B) Co(II) Octahedral and Tetrahedral Complexes:
(B.M.)
J.lobs J.ls (B.M.)
ra
Octahedral (h.s.)' complexes (~g ei, 4TIg ): 4.8-5.2 3.87
Octahedral (I.s.) complexes (t~g e~, 2Eg): 1.8-1.9 1.73
ib
Tetrahedral complexes (e 4tl, 4A 2): 4.2-4.8 3.87
yl
J.lobs: 0/1 (h.s.) >Td > 0h (1.s.)
m
• The high-spin octahedral complexes of Co(II) can make an orbital contribution to the observed
i
magnetic moment. The excited state (t 2 e~) is also suitable to make an orbital contribution through the
he
spin-orbit coupling interaction (A = -ve, i.e. positive contribution).
• In the tetrahedral complexes (e 4 ti), the orbital contribution is quenched in the ground state but
lc
some orbital contribution can be introduced from the excited states (e 3 t1; e3 ti 4p l) via the spin-orbit
coupling (interaction) (A = -ve, i.e. positive contribution).
ea
Let us illustrate for [CoCI 4]2- for which the first excited T-term (4T2 ) resides 3100 cm- I above the
ground state (4A 2 )
th
4 x -172)
= ( 1- x 3.87 B.M. = 4.73 B.M.
e/
f.leff
3100
• J..I.obs (h.s. 0h' COIl) ) J..I.obs (Td , COIl): Both the systems possess the same number of unpaired
t.m
electrons but the high spin octahedral complexes record the higher magnetic moment. In th_e high-spin
octahedral complexes, both the excited and ground state make the positive orbital contribution. But in
the tetrahedral complexes, only the excited state makes a slight positive contribution. The orbital
e
contribution from the ground state is more significant than the contribution from the excited state. It
er
makes J.lobs (h.s. 0h) > J.lobs (Td )

• The low-spin octahedral complex (t 2: e~) does not have any orbital ct)ntribution from the ground
H
state. It can slightly increase the magnetic moment through the spin-orbit coupling interaction, i.e.
mixing of the excited state (t2~ei which is capable of making an orbital contribution) with the ground
k
state.
lic
In the low-spin Co(II) octahedral complexes, the high lODq value makes the spin-orbit cou-
pling contribution negligible. It is illustrated below for [CO(N0 2)6]4- (2E g ) (A = -515 cm, 10Dq
= 12,000 cm- I )
C
f.lejJ = ( 1-
2X-5I5) x 1.73 B.M. = 1.87 B.M.
12,000
Thus, J.leff is very close to J.lspin-only.
Note: Sometimes the configurational equilibrium, Oh(h.s.) ~ Td may complicate the interpreta-
tion of the magnetic data (cf Sec. 8.26).
Sometimes, in the octahedral complexes of Co(II), the spin state isomerism leading to the low spin
~ high spin equilibrium may also complicate the interpretation of the magnetic data (cf Secs. 8.24-26).
• JJ.obs: 0h (h.s.) (~ge~) ) ) Oh(l.S.)(t~ge~)

No. of unpaired electrons: 3 1
I-ls (B.M.): 3.87 1.73
Orbital Contribution
(from ground state): Yes No No
ry
Orbital Contribution
from the excited states: Yes Yes Yes
ra
(via spin-orbit coupling)
• Magnetic moment of [COX4]2- (e 4 t23 ; (X- = halide and pseudo-halide).
ib
4A 2 )
yl
[CoX 4 J-: SCN- CI- Br- I-
m
,.., flobs (B.M.) : 4.4 4.6 4.7 4.8
There is no orbital contribution from the ground state (e4~) but it can experience the orbital contri-
he
bution from the excited state (e 3 t1; 4T2 ) via the spin orbit-orbit coupling.
flefj = (1 - ~JflsPin-OnlY'
10Dqt .
A lc= -ve.
ea
It leads to: 1l1f = 3.87 - 15.5A. ,taking Ilspin-only = 3.87 B.M. for three unpaired electrons.
e 10DQt .
th
The spin-orbit coupling constant (A which is negative) does not vary significantly from one complex
e/
to another. This is why, JJ.efT bears an inverse linear relationship with lODqt (i.e. crystal field strength).
The above relation indicates that with the increase of 10Dqt value, I-left' should decrease and move
t.m
towards the J.!spin value. Experimentally, it happens so. Here, we have ignored the effect of orbital
reduction factor (k).
The lODqt value varies as: SCN- > CI- > Br- > I- and JJ.efT varies as: I- > Br- > CI- > SCN-
(C) Co(II) square planar complexes: The electronic configuration of the low spin Co(II)
e
complex is:
er
( dXz.' dyz. ) 4 ( d: 2 )2 ( d xy ) I .l.e. egai'gb2g

4 / I
H
There is only one unpaired electron. The filled eg-orbital set, i.e. eg4 , cannot make any orbital contri-
bution but the excited state having the electronic configuration, (dX2 ' dy .)3 (dz. 2 )2 (dXy )2, i.e. e~ aT g b~g can
k
make an orbital contribution through the spin-orbit coupling. Here it may be noted that the dxz and dyz
lic
orbitals consisting of the eg set can be lTIutually converted through rotation by 90 0 about the z-axis. This
is why, a low spin square planar complex of Co(II) shows I-lobs greater than I-lspin- However, it may be
C
noted that this orbital contribution from the excited state is not sufficient to explain the so high I-leff
(with respect to I-lspin) value.
[Co(salen)]: I-lobs = 2.25 B.M.; [Co(bigH)2]S04: I-lobs = 2.50 B.M. (ef I-lspin = 1.73 B.M.)
To explain the anomalous magnetic moments of the square planar complexes of Co(II), contri-
bution of the intermediate spin states and spin admixed states may be considered (ef Sec. 8.25).
(D) Ni(II) octahedral and tetrahedral complexes
I-lspin (B.M.) I-lobs (B.M.)
Octahedral complexes (t~g e,~, 3A 2g ): 2.83 2.90-3.50

Tetrahedral complexes (e 4 ti, 3T\): 2.83 3.2-3.8
• In the octahedral complexes, there is no orbital contribution from the ground state (t~g e;) but an
orbital contribution from the excited state (t2~ e;,
3T2g ) can be introduced via the spin-orbit coupling
interaction.
Il eff = (1- ~JllsPin-OnlY'

10Dq
A = -vee
ry
It makes J.lobs > J.lspin-onIy·
ra
• In the tetrahedral complexes, the ground state (e 4 tj) is capable of making an orbital contribution
and the excited state (e 3 ti) can also make an orbital contribution via the spin-orbit coupling interaction.
ib
However, the orbital contribution from the ground state is more important.
J.lobs: Td (orbital contribution from both the ground and excited states) >0h (orbital contribution only
yl
from the excited state).
(E) Distorted and regular tetrahedral complexes of Ni(ll) (e 4t1): For the regular tetrahedral ge-
m
ometry, the ground state can make the orbital contribution. In addition to this, the orbital contribution
he
from the excited state can also be introduced through the spin-orbit coupling. But very often, the
regular tetrahedral geometry is distorted to C2v symmetry and the T] ground state term transforms into
three singlets A b B] and B 2 (i.e. orbital degeneracy is lifted):
lc
T] (Td ) ~ A 2 + B I + B 2 (C2v ), (see Correlation Table, Sec. 7.23)
ea
The A b B I and B 2 terms cannot make any orbital contribution. Morever, the magnetic property of
T-term is highly temperature dependent (ef Sec. 8.20) but the magnetic property arising from the A 2, B]
and B2 terms is not temperature dependent. This is why, for Ni(ll), the magnetic moment of a regular
th
tetrahedral complex is higher than that ofa distorted tetrahedral complex and the magnetic moment
e/
of a regular tetrahedral complex is highly temperature dependent while the magnetic moment of a
distorted tetrahedral complex shows an insignificant temperature dependence.
t.m
Regular tetrahedral complexes of Ni(II): J.lobs =3.6-4.0 B.M. (significant temperature dependence)
Distorted tetrahedral complexes of Ni(II): J.lobs = 3.0-3.5 B.M. (insignificant temperature
dependence)
e
The magnetic moment of the complex (Et4 N)2[NiCI 4] is 3.9 B.M. at room temperature and it is
er
highly temperature dependent. It indicates that [NiCI 4]2- in the complex is possessing the regular
tetrahedral structure. The magnetic moment of the complex, (Et4 N)2[NiI4 1 is 3.5 B.M. at room tem-
H
perature and it does not change significantly with temperature. It indicates that [Nil 4]2- in the complex
possesses a distorted tetrahedral structure.
k
Considering this fact, Nyholm had suggested an inverse relationship between the J.leff and extent of
lic
distortion in the tetrahedral geometry of Ni(II). The seriously distorted complex, NiX 2· 2PPh 3 shows
J.leff = 3 B.M. at room temperature.
C
Note: Sometimes, the configurational equilibrium like octahedral ~ square planar, square planar
~ tetrahedral may complicate the interpretation of the magnetic properties of the Ni(ll) complexes.
This may lead to an anomalous magnetic property of the Ni(ll) complexes. This aspect has been
discussed in Sec. 8.26.
(F) Cu(ll) octahedral complexes (t 2; ei, 2Eg ) and tetrahedral complexes (e 4 ti, 2T2 ): Between
these two, an orbital contribution from the ground state exists in the tetrahedral complexes but not in
the octahedral complexes. However, an orbital contribution from the excited state (tfge,:) can occur via
the spin-orbit coupling in the octahedral complexes but this remains absent in the tetrahedral complexes
for which the excited state (e 3 t~) is unable to make any orbital contribution. The orbital contribution
from the ground state is more important than the orbital contribution from the excited state. It makes:
J.lobs (Td ) ) J.lobs (Oh)·
8.19 MAGNETIC PROPERTIES OFTHE LANTHANIDES AND ACTINIDES

8.19.1 Magnetic Properties of the Lanthanides
ry
The trivalent lanthanides (La3+ to Lu 3+) bear the general electronic configuration:
[Pd]4.f 5s 2 5p 6, (n =0 - 14)
ra
(a) No crystal field effect: The magnetic properties of the lanthanides arise from the 4.f electrons
(cf for the first transition series, the magnetic properties arise from the 3(/1 electrons). The 3d, i.e.
ib
(n - l)d orbitals are better exposed to the crystal field environment and the crystal field effect is quite
yl
important to quench the orbital contribution (i.e. L = 0 and J.lJ reduces to J.ls). On the other hand, the
41, i. e. (n - 2)f orbitals of the lanthanides are deeply seated and effectively shielded by the 5s and 5p
m
orbitals. Consequently, the crystal field effect to quench the orbital contribution (i.e. L = 0) for the
lanthanides is not important. In fact, crystal field effect in the lanthanides is approximately only one-
he
hundredth of that observed for the 1st transition series metal ions.
lc
Magnetic Properties: Lanthanides vs. 1st transition series metal ions
ea
• For the lanthanides, the crystal field effect is less important because the 4f orbitals are
deeply seated and effectively shielded by the outer 5s and 5p orbitals. This is why, the 4f orbitals
are poorly influenced by the crystal field.
th
• Crystal field effect is more important for the 1st transition series metal ions to quench the
e/
orbital contribution to the magnetic properties through the crystal field splitting of the 3d-orbitals.
• Crystal field effect to split the 4f orbitals to quench the orbital contribution to the magnetic
t.m
properties for the lanthanides is relatively less important.

• Free ion term (lanthanides) vs. crystal field terms (transition metal ions): For the lantha-
nides, crystal field splitting of the free ion term is not significant. This is why, the free ion terms
e
determine their magnetic properties. On the other hand, for the transition metal ions, the crystal
field splits the free ion terms and these crystal field states determine their magnetic properties.
er
• Because of the poor shielding character of the 4f orbitals, the increased Z* makes the spin-
H
orbit coupling constant very high for the lanthanides. Thus the coupling of the Land S vectors
is very much efficient to make J, a good quantum number for the lanthanides. On the other hand,
k
because of the small values of the spin-orbit coupling constant, J is not a good quantum number
for the 1st transition series metal ions.
lic
• In general, for the lanthanides, the magnetic moment is given by:

C
J.lJ =gJ)J(J+l) B.M. (contribution from the ground state J generated from the free ion
term and assuming ~EJ, J+I (multiplet width) ) ) kBT)
For the first transition series metal ion complexes (L = 0, i.e. quenching of the orbital contri-
bution), the above equation generally reduces to:
J.lspin-only =J.ls =ge)S(S+l) B.M.=)4S(S+1) B.M.

However, sometimes, there may be some partial orbital contribution from the ground and
excited states characterised by the T-term.
(b) High spin-orbit coupling constant: Secondly, the poor shielding character of the deeply seated
4f-orbitals makes the effective nuclear charge (Z*) very high. Consequently, the spin-orbit coupling
constant (A) is quite high for the lanthanides (cf. Table 8.13.4; for the trivalent ions of first transition
series, S:: : 150 - 800 em-I; for the trivalent lanthanides, s·::::: 650 - 3000 em-I). Because of this high
value of spin-orbit coupling constant, the L (resultant orbital angular momentum) and S(resultant spin
J =) J (J + 1) ~.
ry
angular momentum) vectors can effectively couple to generate the J vector Thus
2It
for the lanthanides, J is a good quantum number (cf. for the 1st transition series metal ions, coupling
ra
between the Land S vectors is not so efficient because of the lower values of the spin-orbit coupling
ib
constant and consequently, J is not a good quantum number for them).
(c) J.l.i for the lanthanides (assuming contribution only from the ground state J, i.e. AEJ,]+l »
yl
kBT): For the lanthanides, J is a good quantum number and in general, their magnetic moment is given
m
by the following equation.
Ileff = IlJ = gJ )J (J + 1) B.M.
he
(d)fO,f andf14 systems: For the systems,fO andfl4, S = L = 0 (i.e. J = 0), i.e. JlJ = O. For f, L =
0, and J = S. Consequently, the above equation is automatically reduced to:
lc
lletT = Ils = ge)S(S + 1) B.M. (for f7, L = 0 and J = S)
ea
=)4S(S+I) B.M. (ge =2)
th
=)n(n+2) B.M.
Here, n denotes the number of unpaired electrons.
e/
For La 3+ , Lu 3+, n = 0, thus, Ils = )0(0 + 2) B.M. = O.

t.m
For Eu 2+ and Gd +, n = 7 and Jls = )7 (7 + 2) B.M. =163 B.M. = 7.9 B.M.

3
Table 8.19.1.1 Magnetic moments of the lanthanides

e
4f' (n) M 3+ L S Ground gJ JlJ (H.M) Jls (B.M) Jlobs. (H.M.)

=gJ~J(J+l)
er
(= n12) state (ground

term state)
H
0 La 3+ 0 0 ISO 1 0.0 0.0 Diamagnetic

1 Ce 3+ 3 1/2 2F 5/ 2 6/7 2.54 1.7 2.3-2.5
k
2 Pr3+ 5 1 3H
4 4/5 3.58 2.8 3.4-3.6
lic
3 Nd 3+ 6 3/2 41 9/ 2 8/11 3.62 3.9 3.5-3.6

4 Pm 3+ 6 2 sI 4 3/5 2.68 4.9
C
5 Sm 3+ 5 5/2 6H s/2 2/7 0.84 5.9 1.5-1.6

6 Eu 3+ 3 3 7F
o 1 0 6.9 3.4-3.6
7 Gd 3+ 0 7/2 8S 7/ 2 2 7.94 7.9 7.8-8.0
8 Tb 3+ 3 3 7F
6 3/2 9.72 6.9 9.4-9.6
9 D y 3+ 5 5/2 6H
IS12 4/3 10.63 5.9 10.4-10.5
10 Ho 3+ 6 2 sI 8 5/4 10.60 4.9 10.3-10.5
11 Er3+ 6 3/2 41 15 / 2 6/5 9.57 3.9 9.4-9.6
12 Tm 3+ 5 1 3H
6 7/6 7.63 2.9 7.1-7.4
13 Yb 3+ 3 1/2 2F 7/ 2 8/7 4.50 1.7 4.4-4.9
14 Lu 3+ 0 0 ISO 1 0 0 Diamagnetic
(e) Sm(lll) and Eu(III): Except Sm(lll) and Eu(III), all other lanthanides fairly agree with the
calculated magnetic moments (Jlj) (Table 8.19.1.1). In the case of Sm(lll) and Eu(III), the multiplet
width (t:£j.J+I) is comparable to kBT while for the other lanthanides, the condition, multiplet width»
kBT is maintained. It indicates that for Sm(lll) and Eu(III), the excited states along with the ground state
are thermally populated at normal temperature but for the other lanthanides, only the ground state is
populated. Thus, except for Sm(lll) and Eu(III), the relation Jleff= Jlj for the ground J-Ievel is maintained.
ry
s
( H%J
ra
~
J= ~ 7 (7 F5 )
2 F3
J=5 J=5
ib
(515 ) J=3
(~)A
yl
2
3A
m
s ,
he
(H~ ) ~ 7
2
F2
5A J= ~ J=2
6A
2
lc
2A
ea
(2-)A
'=r:
7
2 F
1
(5 14 ) .,
th
(SH9-) (F ) A } ground
o (7
Fs )
~ state
2
J=4 J= J=O J=6
2
e/
Pm 3+ 8m
3+ Eu 3+ Tb 3+
t.m
(4(4) (4(5) (4(S) (4(8)
Fig. 8.19.1.1 Qualitative representation of the energy levels of Pm 3+, Sm 3+, Eu 3+ and Tb 3+. Energy separation, i.e.
multiplet width, ~EJ. J+I = A(J + 1) (Lande interval rule)
e
For Sm(lll) and Eu(III), the equation under the condition, t:£j,j+I :::: kBT is to be used. The cases of
er
Sm(lll) and Eu(lll) are discussed below and compared with those of Pm(lll) and Tb(III).
(0 Pm(III) (414): S/4 (L = 6, S = 2), J = 4, 5, 6, ... , 8.
H
t:£j.J+I = A(J + 1) (i.e. Lande Interval Rule). Thus the first excited state (J = 5, i.e. sIs) lies above the
ground state (J = 4) by 5A, i.e. t:£4,S = 5A = 5 x 250 cm- I = 1250 cm- I (assuming A = 250 em-I) » kBT
k
:::: 200 em-I.

lic
5 7 9 11 13 15
(g) Sm(lll) (4.111'5 ): 6
H S12 (L = 5, S = 512), J =-, -. -, -, -, -
22'2222
C
The first excited state (J = 7/2 i.e. 6H712 ) lies above the ground state (J = S/2) by '2 A only, i.e.
2
~S/2 , 7/2 ='2A='2x240 cm- I =840

2 2
em-I.
(h) Eu(lll) (4.r): 7Fo (L = 3, S = 3), J = 0,1,2,3,4,5,6. The first excited state (J = 1 i.e. 7F I ) lies
above the ground state (J = 0) by 1A i. e.
t:£O,l = A :::: 230 em-I:::: kBT (= 200 em-I).
(i) Tb(III) (4.f): 7F6 (L = 3, S = 3), J = 6, 5, 4, 3, 2, 1,0

The first excited state (J = 5 i.e. 7F s) resides above the ground state (J = 6) by 6A i.e.
~s, 6 = 6A = 6 x 202 = 1212 em-I.
For Sm(III), (A = 240 em-I), energy separation between the ground and first excited state is
840 cm- 1 (= ~ A) and for Eu(III), the said energy separation is about 230 cm~l (= A). Thus, for Eu(III),
ry
the energy separation is close to the thermal energy (kBT:::: 200 em-I) and consequently, the first excited
ra
state (J = 1) and even the second (J = 2) and third (J = 3) excited states are thermally populated to some
extents. For, Sm(III), only the first excited is populated to some extent. In such cases, each J-Ievel
ib
contributes to the magnetic moment according to its population density.
• Sm(III): Let us illustrate for Sm(III) where the ground state (J = 5/2 i.e. 6Hs12 ) and the first excited
yl
state (J = 7/2 i.e. 6H712 ) are supposed to be populated according to Boltzmann distribution law and these
m
two levels will mainly contribute to XM according to their population density. The higher excited
states (Le. J =9/2, 11/2, etc.) are poorly populated and they will contribute according to their population
he
density. Thus their contribution is relatively small and these can be ignored.
_ 1+ J (J +1) + S (S + 1) - L (L + 1)
gJ -
lc
2J + 1
ea
5
For Sm(III), L=5 , s=-
2'
th
g 5 = 0.286, g 7 = 0.825
e/
J=- J=-
2 2
By using the following relation (ignoring the contribution of 2 nd order Zeeman effect).
t.m
XM = ~::; [; l~;ff =[; ]~2 ,i.e. ~eff =[ ; YB.M. (cf. Sec. 8.14)
e
er
L+S
x= L g7 J (J+l)(2i+l)exp(-8E J /k BT)
H
J=IL-si
L+S
L
k
y= (2J+l)exp(-6.E J /k B T)
lic
J=IL-si
~J = energy of a particular i-level with respect to the ground level (i.e. J = 5/2 in the present case).
C
X = (0.286)2 X(%) x (1 + %)(2 x %+ 1) exp (0)
+(0.825)2 X(~)(1+~)(2X~+1)eXP( -~x k> )+......
Y=(2X%+1)eXP(0)+(2X~+1)eXP(-~x k~T )+......

By using these values, we get J-leff ::::: 1.3 B.M. at 300 K. This value is in good agreement with the
experimental value 1.54 B.M.
[Note: In the above expression 'of only contribution of the 1st order Zeeman effect from the
J-leff'
different J-Ievels is considered to the magnetic moment according to their Boltzmann population densities.
In addition to this 1st order Zeeman effect, there is a 2nd order Zeeman effect from the higher J-Ievels
(cf. Sec. 8.22.2).
ry
However in our calculation, contribution of this 2 nd order Zeeman effect is ignored. By taking the 2 nd
ra
order Zeeman effect, J-leff at 300 K becomes about 1.38 B.M.]
~J (J + 1) B.M. (contribution only from the ground state J = %). then
ib
If Jleff is calculated by gJ
yl
the value becomes -0.84 B.M.
m
i.e. JlejJ =JlJ =0.286~%(%+1) B.M. =0.84B.M.
he
This situation may be experienced experimentally only at very low temperature when the ground
level (J = 5/2) is only thermally populated. At this condition, a small contribution may also occur from
lc
the 2nd order Zeeman effect (Sec. 8.22.2).
ea
• Eu(III): In the case of Eu(III), XM may be calculated as follows according to the thermal popu-
lation densities of the different levels 7 Fa (ground state), 7 FJ, 7 F2, .••
th
_ 1+ J (J + 1) + 5 (5 + 1) - L (L + 1)
e/
gJ - 2J(J + 1)
t.m
0+3x4-3x4
gJ=o(L=3,S=3)=1+ 0 =1.0
(L = 3, S = 3) = 1+ 1x 2 + ~ : ~ -
e
g J =1 3 x 4 = 1.5
er
x = 12 X 0(0 + 1)(2 x 0 + l)exp(O) + (1.5)2 x 1(1 + 1)(2 xl + l)exp(-~J +

H
.
kBT
k
= (2 x 0 + l)exp(O) + (2 xl + l)exp(-~J +
lic
Y .
kBT
C
By using these values (ignoring the 2nd order Zeeman effect, Sec. 8.22.2), we get J-leff (at 300 K) 3.5
B.M. which is in good agreement with the experimental value 3.6 B.M.
It may be noted that J-lJ calculated as follows becomes zero.
Ileff = III = gl=O)J(J + 1) B.M. = 0 (assuming the ground state J = 0 to contribute only)
In fact, at very low temperature when the ground level (J = 0) is only populated, the observed
magnetic moment is almost zero as expected from the above equation. At very low temperature,
Eu(III) shows only a small residual paramagnetism arising from the 2nd order Zeeman effect (Sec.
8.22.2).
MAGNETOCHEMISTRV:MAGNETIC PROPERTIES OF METAL COMPLEXES 1153
11
10
9 f.!J (J for the ground state)
8
~
/
7 ~
~
/
ry
~
ai 6 f.!s ~
c:
:.:=- 5 ~,//
ra
:::1.
4 /
~
i 3
ib
2
yl
1
0
m
La Ce Pr Nd Pm 8m Eu Gd Tb Dy Ho Er Tm Vb Lu
Fig. 8.19.1.2 Magnetic moments (at 300 K) of the trivalent lanthanides. • represents Ill; • represents the corrected
he
values for Sm(III) and Eu(III); dashed curve (----) represents the Ils values.
• Other Ln(III): For Tb(III), Pm(III) and other lanthanides, ~EJ. J+l » kBT and the equation of ~J
lc
nicely works. For Sm(III) and Eu(III), it requires some special correction. The plot~of Jlobs vs. f' is a
double humped curve (cf Fig. 8.19.1.2).
ea
8.19.2 Magnetic Properties of the Actinides
th
In the actinides, the 5f orbitals are relatively better exposed (cf relativistic expansion, Vol. 1) to the
ligands than the 4f orbitals of lanthanides. This is specially true for the early members of the actinides.
e/
Thus in general, the Sf orbitals ofthe actinides are affected more by the crystal field compared to the
4f orbitals ofthe lanthanides. But obviously, the crystal field effect is not so high as in the case of first-
t.m
transition series. The relative crystal field effect is:

1st Transition series » Actinides Lanthanides
metal ions (5f-orbitals) (4f-orbitals)
e
(3d-orbitals)
er
Relative ratio:· 100 10 1

Thus, orbital contribution is quenched by the crystal field to some extent in the case of actinides
H
while this quenching effect is virtually absent in the case of the lanthanides. The magnetic moment
calculated by JlJ expression is somewhat larger than the experimental values for the actinide complexes,
k
This illustrated in Table 8.19.2.1.

lic
Table 8.19.2.1 Magnetic behaviour of actinide complexes

C
Sf' Ion Ground State Term J.lJ (H.M.) J.lobs (B.M.)
5f U(V), Np(VI) 2F
5/2 2.54 1.7-2.0
5f U(lV), Np(V) 3H
4 3.58 2.2-3.2
5f Np(lV) 41 9/2 3.61 2.7-2.9
5f Pu(lV) 51
4 2.67 1.7-1.9
5f Pu(III) 6H
512 0.85 1.1-1.2
5f Am(lII) 7Fo 0 1.5-1.6
5f Cm(III) 8S 7/2 7.95 7.8-9.0
Here it is striking to note that, for Pu(lll) (Sf5) and Am(lll) (S.f), the calculated J.lJ value signifi-
cantly deviates from the experimental value. In fact, in these two cases, aE1, 1+1 (i.e. multiplet width)
is comparable to the thermal energy (kBT). Thus, besides the ground state, the excited states (differering
in I-values) will have some population density controlled by the Boltzmann distribution function as in
the case of Sm(lll) (4/) and Eu(lll) (4/6) of the lanthanides. This is why, for Pu(lll) and Am(III),
different I-levels contribute to XM according to their population density controlled thermally.
ry
Sm(llI) (4f5), Eu(lIl) (4f6 ) vs. Pu(lIl) (5f5), Am(lIl) (5f6 )
ra
Magnetic behaviours of these two trivalent lanthanides are comparable with those of these two
ib
trivalent actinides. In both the cases, the condition, multiplet width:::: kBT is maintained.
yl
8.20 COMPARISON OFTHE MAGNETIC PROPERTIES OFTHE A, E AND TTERMS:
m
TEMPERATURE DEPENDANCE OFTHE MAGNETIC PROPERTIES
he
8.20.1 Magnetic Properties of the Complexes with the A and E Ground State Terms
Orbital contribution from the ground state: We have already mentioned that for the complexes of A
lc
and E ground state terms, there is no orbital contribution from the ground state. The orbital contribution
ea
is totally quenched.
Orbital contribution from the excited T -state through spin-orbit coupling: For the tetrahedral
and high-spin octahedral complexes, it leads to:
th
-(1-~) a = 2 for E term Energy difference between the

e/
f.leff - 10Dq f.lspin'

ground state and first excited
a = 4 for A term
t.m
state is 10Dq i.e. E( A2 ) -- E (T2 )

A = -ve for cJ6 - tP }
A = +ve for d l - d4 = 10Dq; E(E) -- E(T2 ) = 10Dq.
e
Table 8.20.1.1 Values of spin orbit coupling constant and uA-values for some representative ions of 1st
transition series
er
Metal ion Symmetry Ground state term A (em-I) aA (em-I)

H
y4+(d l ) Td 2£ 250 500

k
Cr 3+(d3 )
°Il 4A 2g 92 368
lic
Cr 2+(tf) 0" 5£g 58 116

Fe 2+(lF) Td 5£ -100 -200
C
Co 2+(d7 ) Td 4A 2 -172 -688

Co 2+(J?) Oil (1.s.) 2£g -515 -1030
Ni 2+(tfS) 3A 2g -315 -1260
0"
Cu 2+(dJ)
°Il 2£g -830 -1660
The 10Dq value (energy difference between the ground state and first excited state of T-term) is in
the order of 10,000 cm- l which is too large compared to the thermal energy kBT.
Thus, the excited state which undergoes mixing with the ground state is not thermally accessible. In
.
other words, the population density of the excited state does not depend on the temperature. This is
why, this spin-orbit coupling contribution does not depend on the temperature (Table 8.20.1.2).
Here it is worth mentioning that the ground A and E terms do not undergo splitting through the
spin-orbit coupling.
Magnetic properties: A, E-terms VS. T-term

• For the A and E terms, there is no orbital contribution from the ground state and the excited state
ry
(if T-term) can introduce the orbital contribution through the mixing with the ground state via
ra
the spin-orbit coupling. However, the spin-orbit coupling can make a negative or positive
contribution to J.leff depending on the sign of A.
ib
• For the A and E terms, fleD" is insensitive to the temperature variation.
• For the T-term, the ground state can make an orbital contribution. It makes J.leff much greater
yl
than J.lspin.
• For the T-term, is sensitive to the temperature variation.
m
fleD"
he
Table 8.20.1.2 Magnetic moments of some octahedral and tetrahedral complexes with A and E ground state
at different temperatures (magnetic moment does not vary significantly with the temperature variation)
Complex Electronic
Configuration
Ground
State
lc JJ.eff
calc.
(B.M.)
JJ.spin
(B.M.)
JJ.obs (B.M.)*
ea
80K 300 K
[VCI4] Td , (e\) 2E 1.62 1.73 1.71 1.68

th
K2S04, Cr2(S04h· 12H2O 0h (t~.R) 4A 2g 3.80 3.87 3.84 3.85

K3 [MoCI 6] 0h (t~R) 4A 2g 3.65 3.87 3.62 3.78
e/
CrS04· 6H20 0h (t~R e~) 5E

R 4.87 4.89 4.84 4.82
t.m
[Mn(acac )3] Ojz (~g e~) 5Eg 4.87 4.89 4.76 4.85
K2S04, MnS04· 6H20 0Jz (~g e;) 6A\g 5.92 5.92 5.90 5.90
Cs 2[CoCI4] Td (e 4 ti) 4A 2 4.70 3.87 4.50 4.60
(Et4Nh[FeCI 4] Td (e 3 ti) 5E 5.92 4.89 5.80 5.90
e
K2Ba[Co(N0 2)6] 0h (~g e~) 2Eg 1.86 1.73 1.75 1.80

er
(NH 4hS04' NiS0 4· 6H 2O 0h (~g e;) 3A 2R 3.22 2.83 3.30 3.30

(NH 4hS04' CUS04' 6H 2O 0" (~g ei) 2E 1.97 1.73 1.91 1.90
H
* The calculated value by egn. J..leff. = (l - uA/l ODq)J.!spin nicely agrees with the observed value. This relation indicates
k
that for the higher 10Dq value, J..leff will be more close to J..lspin' In fact, J..lobs for [Ni(NH 3)6]2+ is close to J..lspin while for
[Ni(OH 2)6f+, J..lobs is greater than J.!spin. It is due to the higher 10Dq value for NH 3 compared to that for H20 as the
lic
ligands.
C
8.20.2 Magnetic Properties of the Complexes with the T-ground State

The complexes with the T-ground state can enjoy an orbital contribution to some extent. It makes
J.leff ) J.lspin.
Spin-orbit coupling can split the T-terms (ef Fig. 7.7.4.2, Sec. 8.20.3). These are summarised below:
Crystal field state: 3T}(g) 4T}(g) 5T}(g) 2T2(g) 3T2(g) 5T2(g)
~ ~ ~ t ~ ~
Spin-orbit coupling components: 3 3 3 2 3 3
Here it may be noted that the A and E terms do not undergo splitting by the spin-orbit coupling.
It has been already pointed out that the A and E terms cannot retain the orbital angular momen-
tum (i.e. L = 0) and they cannot make any orbital contribution, but the T-terms can retain the orbital
angular momentum (i.e. L #0) and they can make the orbital contribution. This is why, the Land S
vectors of a T-term can generate the different ]-values.
Energy separation among the spin-orbit coupling components (arising from the T-term) is more or
less comparable to the thermal energy kBT. Population density at these different energy levels is governed
ry
by the Boltzmann distribution law. In other words, their population density is thermally controlled.
Thus contribution of these energy levels to the magnetic properties is highly dependent on the
ra
temperature. This sensitive temperature dependence of J.lobs of the T-terms is shown in Table 8.20.2.1.
ib
Among the different examples, the octahedral complexes ofV(III) (cP, t2~) do not show the temperature
dependent magnetic moment though they possess the ground state 3T1R term. This is an exception and
yl
this anomalous behaviour of V(III) (t1g ) is explained in the following ways:
ti
m
(i) The R set experiences the J.T. distortion. Consequently, the ground T-term splits into the A and
E terms. The A and E terms do not experience any splitting through the spin-orbit coupling.
he
Moreover, these A and E terms fail to make any orbital contribution.
(ii) Delocalisation of the electron into ligand orbitals reduces the orbital contribution to the metal.
lc
Table 8.20.2.1 Magnetic properties of some complexes having the T-ground state. (Magnetic moment
ea
changes apprecialbly with the change of temperature)
Compound Electronic Ground Ilspin !Jobs (B.M)
th
Configuration state (B.M.)

80K 300K
e/
Cs 2[YCI 6] y 4+, d t (t~g) 2T2g 1.73 1.40 1.80

t.m
CsTi(S04h·12H 2O Ti J+, d l (t~g) 2T2g 1.73 1.55 1.85

(NH 4hS04' Y2(S04h· 24H 2O yJ+, d 2 (t~g) 3T
1g 2.83 2.78 2.80
K 3 [Mn(CN)6] 3
Mn +, d 4 (fig) JT tg 2.83 3.30 3.50
Ru 4+, d4 (fig)
e
K 2 [RuCI 6 ] JT 1g 2.83 1.63 2.70

er
K 2 [OsCI 6 ] OS4+, cf (fig) 3T

1g 2.83 0.80 1.50
K 3 [Fe(CN)6] Fe J+, cF (t~g) 2T2g 1.73 1.90 2.25
H
K4[Mn(CN)6]·3H 2O Mn 2+. d 5 (f~g) 2T

2g 1.73 2.0 2.20
[Ru(NH J)6]CI 3 3
Ru +, d 5 (~g) 2T
2g 1.73 1.85 2.20
k
(NH 4 hS04' FeS04' 6H 2O Fe 2+, J6 (fig e,~) 5T

2g 4.9 5.35 5.47
lic
(NH 4 hS04' CoS0 4· 6H 2O Co 2+, d 7 (ti g e,~) 4T

tg 3.87 4.60 5.10
(Et4Nh[NiC1 4] Ni 2+, d 8 (e 4 ( 4 ) JT 1 2.83 3.25 3.90
C
8.20.3 Magnetic Properties of the 1st Transition Metal Ion Complexes (with the T-ground
state) at DifferentTemperatures
(A) Calculation of L-value of T-terms: We have already seen that a T-term can retain its orbital
angular momentum (i.e. L ~ 0). This is why, a T-term can generate the i-values through the coupling
of Land S vectors. Determination of L-value of a T-term is simplified by making a correspondence
between the T- and P-terms (of free ion). The three fold orbital degeneracy is maintained for both the
T and P terms. The t 2 (R) orbitals, similarly, correspond to the p-orbitals of the free ion.
It can be shown that though the total wave function of the t 2(g) orbitals is not fully equivalent to the
wave function of the p-orbitals, but the wave functions are equivalent in terms of orbital angular
momentum integrals. It may be noted that the magnitudes of the orbital angular momentum of
the t 2(g) and p-set of the orbitals are the same but of the opposite sign. This is why, the energy order
of the J-values of these two sets will be opposite. In other words, splitting of the T-terms by spin-orbit
coupling is obtained by inverting those of the P-terms generated from the same number of p-electrons
ry
as there are d-electrons. Hole formalism rule indicates that spin-orbit coupling splitting of the pn and
p6-n (n < 3) configurations bears an inverted relation. The findings are given below.
ra
2T2g (d l'2g
t leO)
g -
= 2p(p5) ,
3Tlg(~, t2~e~) == 3p(p4), 3TI(cf', e4ti == t1) == 3p(p4)
ib
3TIg (d4, t2;e~; strong field) == 3p(p2), 2T2(tP, e4 ti == !i) == 2p(p5)
yl
According to the hole-formalism
m
2T2g (d5, t2~ e~, strong field) == 2p(pI), rule, t2~ == t2~-n == p6-n ; and pn == p6-n; n < 3
Thus we can conclude that for a T-term, the L value is unity (i.e. L = 1). The spin-orbit coupling
he
splitting patterns of the T-terms have been shown in Fig. 7.7.4.2.
lc
Origin of the T-terms in a cubic crystal field
d l (Oh), A = +ve; d 5 (1.s. 0h), A = -ve; d 9 (T ), A = -ve
= 1/2):
ea
2T2(g) (L = 1, S d
5T2(g) (L = 1, S =2): d 6
(h.s. 0h), A = -ve; d 4 (Td ), A = +ve
th
3TI (g) (L = 1, S = 1): d 2 (Oh), A = +ve; d 4 (1.s. 0h), A = -ve; d 8 (Td ), A = -ve.
4TI (g) (L = 1, S =3/2): d 7 (h.s. 0h), A = -ve; d 3 (Td ), A = +ve.
e/
• A = +ve for t1.2 (i.e. less than half filled); A = -ve for ti,5 (i.e. more than half filled)
t.m
(B) Illustration for the 2T2g term arising from 2D (i.e. t2~): Here we have the values.
131
L = I, S = -, i.e. J = - and -.
e
222
er
3 -I
The t 2g-set is less than half-filled and the energy order will be: J =- < J =- (cf in terms of the
2 2
H
sign of the orbital angular momentum integrals, there is a negative correspondence between the t 2g and
p-orbitals, cf Sec. 8.13).
k
The energy difference between the states defined by J =i and ! is given by i2 A (Lande interval
lic
2 2
rule, cf Sec.8.13).
C
Multiplicity (= 2J + I) of the J =~ state is 4 while for the J =~ state, it is 2. According to the

2 2
barycentre rule (ef Sec.8.13), if the J =i state is lowered by x with respect to the unsplit 2T2g set then
2
the J = ±
state will be raised by (3 A - x ) i.e.
2
4X=2(3A
2
-x).' or X=~2
2
Eg
,~------
I
I
I
I
I
I
I
I
I Splitting
I
Splitting by magnetic
ry
I
I
I
by spin-orbit field
I
I
coupling ~
ra
~\ ~
", J=- , ,/' +~
ib
2
(g = 2) E"= + 8~2 E ' = A
"
,
I---r--------.:.' ,
I ,
I 3A JI tJ
yl
\ I ,
\ II ' _
\ I
\ 1 I -~
m
\ (L = 1 S =-) I
"\ ' 2I I I
he
~29
lc (g = 0)
ea
Fig. 8.20.3.1 Spin-orbit coupling splitting of the 2T2g term arising from the 2D state (t~g i.e. less than half-filled and
A = +ve). Inverted diagram for d 9 , (Td ) and cF (low spin 0h) systems having A = -ve.
th
Note:
e/
(i) A = +ve (for d l , 0h; t2~' less than half-filled); A = -ve (for cP, Td; e4~, more than half-filled);
A = -ve (for d5, low-spin 0h; t2~).
t.m
(ii) J-Ievels are inverted for t2~ (Oh) and e 4 ti (Td ) compared to the J-Ievels of t2~ (Oh). These can be
understood in terms of the sign of A.
The g-value for a particular J-Ievel arising from a T-term can be calculated as follows:
e
= + (2 _ ) J (J + 1) + S (S + 1) - L (L + 1) J:/; 0
er
gJ Y Y 2J(J+l) ,
(Note: The above expression of gJ is not valid for J = 0 because it makes gJ undefined. For J = 0,
H
it is given by: g =y + (2 - y) (L + 1) =4 - y, taking L = 1. The readers are suggested to consult the book,
"The Theory of Transition Metal Ions" by l.S. Griffth, Cambridge University Press, 1971).
k
For, y = 1, we get the common expression of Lande splitting factor. For, y = -1, in the case of t 2g set
lic
(cf a negative correspondence between the orbital angular momentum integrals of the p and t2g orbitals),
it leads to:
C
= -1 + 3{J(J + 1) +S(S + 1) - L(L + I)}

gJ(t 2g ) 2J (J + 1)
= -1 + 3{ J (J + 1) + S (S + 1) - 2} (takin L = 1)
2J(J + 1) , g
It leads to:
• Magnetic behaviour of the t!g system: From these gJ(t 2g ) values, we can conclude that the
ground state (J = %with g = 0 ) fails to make any contribution to the magnetic susceptibility from the
1'1 order Zeeman effect (cf. f.t = gJ~J(J + 1) B.M. = 0)%(%+ 1) B.M. = 0). This is why, thisl-state
ry
is called nonmagnetic or diamagnetic. However, this J =l state can contribute from the second
ra
2
1
=-
ib
order Zeeman effect (i.e. mixing with the excited magnetic state J in presence of a magnetic
2
field) but this contribution is relatively very small.
yl
For the first transition series metal ions, the spin-orbit coupling constant is fairly small (cf. for Ti 3+,
m
A= + 155 cm- I ). This is why, only at very low temperature, the J =llevel is highly populated but at
he
2
ordinary temperature (kBT:::: 200 cm- I , i A:::: 230 cm -1 ), the J = ~ state (i.e. excited state) is significantly
2 lc 2
populated. In fact, at 0 K (where J = ~ is mostly populated), [Ti(OH2)6]3+ and other octahedral
ea
2
=
complexes of Ti(III) show the zero magnetic moment (Ileff 0) ignoring the contribution of 2nd order
th
Zeeman effect. But at a higher temperature, the state J = ~ starts to contribute and f..l becomes positive.
2
e/
• Quantitative treatment for the t!g system: By considering the population density at both
t.m
3
J = 2" and 2"1 levels, XM and f..leff can be calculated by using the Van-Vleck equation (cf. Appendix-
VIII-E). The first order and second order Zeeman coffecients in the present system are as follows:
e
E! = g~J and g = 2, i.e. El =2x ~x ~ = ~ and multiplicity = 2J + 1 = 2 for J = ~

er
2 2
El = g~J = 0 x ~ x l
H
= 0 and multiplicity 2 x l + 1 = 4 for J = l

, 2 2 2
k
8p2 3 8p2 1
2 and E~ = p,
lic
E~
I
=0'I
E~I =- -3A. (for J = -) A E~I = +-
I 3A. I
(for J = -)
2
C
x
XM = Y = 3k T
NAf..l;ff p2 i.e. f.t;jf = N3kAB~2T(X)
Y ; X and Yare evaluated by using the Van-Vleck equation.
B
factor 2 in ~~; denotes the multiplicity of the level (J = ~ ) .

Y = 4ex p (--O_)
kBT
+ 2exp(-~)
2k T
= 2[2 +ex p (- 3X)] where x =~.
B 2 kBT
ry
± =%)
ra
( multiplicity = 21 + I i.e. 2 for 1 = and 4 for 1
ib
(Note: Van-Vleck equation given in Appendix VIII-E:
yl
NA I[(E{)2 /(k B T)-2E{1 Jexp[~h]
m
x
he
Y
XM = Iexp(_ILJ
kBT
Ell =- 8p2 ~
for 1 = interacting with 1 =~;
lc
Ell = + 8p2 for 1 = interacting with 1 = ~ i.e. ~
ea
I 3A 2 2 I 3A 2 2
magnitudes of EP for the both cases are the same but of opposite sign. In computing L(E~)2/(kBn,
th
multiplicity of the level is to be considered. In computing Lexp (- E? J in the denominator, multi-

e/
kBT
plicity (i.e. 4 for J = l, 2 for J = ~ ) is to be considered. In the above calculation,
E(J = l) has been
t.m
2 2 2
taken as zero and E (1 = ±) %

has been taken as + A ).
e
It gives:
er
2[8 + (3x - 8)ex p (- 3X)]

~;ff =~kB; (~)= ~:p; x ~kB; x
H
[ (3X 2)]
A B A X x 2 2 + exp - -
2
k
[8+(3X-8)exp ( - 3X)J
lic
= [ (3
x )2] ,(called Kotani expression)
C
x 2+exp - -
2
· .. Case:
• L Imltmg I H"19h temperature,l.e.T~oo::::}x=
" A
kBT~o,exp ( -2
3X) '" ( 1- 3X) = ( -
22- 3X)
-
2
8+ (3x-8)(2-3x)
2
2 2 16 + 6x - 9x -16 + 24x '" 30x =5 . = 2 25 B M
J..leff = [(2-3X)] x(4+2-3x) 6x l.e. J..leff • ••
x 2+---
2
Il~;iling = JL (L + 1) + 4S (S + 1) = J5 B.M. = 2.25 B.M. ( L = 1, S = ~). (c/. Fig. 8.20.3.4)

• Limiting Case II: Very low temperature i.e. T ~ 0 K
i.e.
A
x= kBT ~ooi.e.exp
3X) ~O
( -2
ry
ra
2 8+(3x-8)xO 4 (. )
Ileff = x(2 + 0) =-:; "" 0, cf· FIg. 8.20.3.4 .
ib
Both the limiting situations are experimentally verified (cf. Fig. 8.20.3.4).
yl
Thus the detailed calculation shows the following result (called Kotani expression) for the t2~
m
configuration.
he
2 8 + (3x - 8)exp ( -¥-) SA)
(x-- kBT -
- kBT
lc
Ileff = x[ 2 + exp ( _ 3; )] B.M. At high temperature, Jleff ~ 2.25 B.M.
ea
At low temperature, Jleff ~ 0 B.M.
th
Jleff is given by the positive square root of Kotani expression for the t2~ configuration. The plot, Jleff
e/
VS. ! = kBT indicates that at higher temperature, Ileff resides on the plateau of the plot i.e. Ileff gets
t.m
x A
saturated.
V(IV) ' ) ( Ti(lIl)
2
e
er
H
Jleffat a particular temperature for

the congeners
(i) Mn(VI) ) Tc(VI) ) Re(VI)
k
(ii) Cr(VI) Mo(V) ) W(V)
i
lic
(iii) A: larger for the heavier congeners.

I
I
C
o 0.2 0.4 0.6 0.8 1.0 1.2 1.4
------+~ ~ ( = ~)
x A
Fig. 8.20.3.2 Temperature dependence of the magnetic moment (J.!) for the 2T2g ground state (i.e. t2~) term in terms of
Kotani plot for the transition metal ions of different series (differing in A-values).
• Kotani plot for the octahedral complexes of Ti(III) (tlg ): For the octahedral complexes of
1
Tj(III), the relative magnitudes of 31. "" 230 cm- (= energy difference between the ground non-
2
magnetic state J =~ and the excited state J =! ) and kBT:::: 200 cm- l (T = 300 K), indicate that in the
2 2
Kotani plot, the plateau is attained at room temperature (ef Figs. 8.20.3.2--4) but only at very low
temperature, it shows the low values of Meff. For the metal ions of high positive charge and heavier
transition metal ions having very high spin-orbit coupling constant, at room temperature, Meff is
significantly low and the saturated value (-1.8 B.M) on the plateau of the Kotani plot is attained at very
ry
high temperature (ef Fig. 8.20.3.2). This is why, at ordinary temperature, for the heavier congeners,
JJetT is relatively smaller (ef Fig. 8.20.3.2).
ra
ib
1.8
yl
m
1.6
he
1.4
lc
r
ea
th
1.2 10.....-_---..1.. ..&..-- ....100.- ......1..- .-..
100 150 200 250 300

e/
-----.~ T (K)
t.m
Fig. 8.20.3.3 Variation 'of the magnetic moment of [VCI6]2- (d 1 i.e. t~g) with temperature. @ represent experimental
value; solid line represents the values obtained from the Kotani equation after considering the tetragonal distortion and
orbital reduction factor (k).
e
er
2.0
H
Ti(lII) (t2~-system, 2T29): Spin-orbit coupling splitting

of the 2T2g state
k
• Ground state (J = 3/2, 9 = 0) is nonmagnetic,

1.2
lic
i.e. no first order Zeeman effect; only a small

2nd order Zeeman effect.
• Excited state (J = 1/2, 9 = 2) is magnetic,
C
i.e. 1st order Zeeman effect contributes to Ilaff'

0.4
100 200 300 400

-----+ T (K)
Fig. 8.20.3.4 Variation of J.!obs with temperature for [Ti(OH2 )6]3+ in Cs-Ti alum
(Note: For the tig configuration, there exists a J.T. distortion. Considering this factor and orbital
reduction factor, the Kotani expression can be further modified to give the better results.)
At very low temperature, i.e. kBT tending to zero, Ileff tends to its limiting value zero (ignoring the
A
contribution of 2nd order Zeeman effect from J = l. ). This has been experimentally realised. At very
2
high temperature (i.e. kBT tending to infinity), Ileff approaches to its limiting value 2.25 B.M. when the
A
ry
orbital and spin motion contribute fully.
ra
!llimiting =~4S (S + 1) + L(L + 1) B.M. =.J5 B.M. =2.25 B.M. ( L =1, S = ±J
ib
However, this limiting value is never attained in reality.
yl
(C) Illustration for the tetrahedral Cu(II) (tP) complexes having the 2T2 ground state (e 4ti): The
m
ground state 2T2 splits into two states J =! and l. (cf Fig. 8.20.3.1). It is having the spin-orbit
he
2 2
coupling constant A = -825 em-I. Because of this negative sign (cf t2 level is more than half-filled for
the tetrahedral complex of Cu(II) while the level is less than half-filled for the Ti(III)-octahedral
t Zg lc
1
complexes), here the ground state is designated by J = 2" (g = 2.0) which is magnetic. But the
ea
excited state designated by J =~ (g =0) is nonmagnetic (i.e. contribution of 1st order Zeeman effect
th
2
to XM remains absent). At a low temperature, the population density at the ground level (J =±J
e/
increases and !leff approaches to 1.73 B.M. (= !lspin) because g =2 for J =! J

(c/.!l =gJ J(J + 1) B.M.
t.m
=2 x J±(± + J 1 B.M. = 1.73B.M.).

e
Thus at 0 K, the tetrahedral Cu(II) complexes attain J1etT = 1.73 B.M. while the octahedral
er
complexes of Ti(III) attain the 0 magnetic moment. This difference arises because for the tP -tetrahedral
H
complexes, the ground state is J =! (g = 2) which is magnetic while for the dI-octahedral complexes,
2
the ground state is J = l. (g = 0 i. e.
k
diamagnetic level).
2
lic
Thus for the Cu(II)-tetrahedral complexes, with the increase of temperature, the population density
C
at J =~ (g = 2) decreases while the population density at J = l. (g = 0) increases and from J =l.,

2 2 2
only the 2nd order Zeeman effect (i.e. the state J = l. interacting with the state J =! ) contribution
2 2
occurs to Ileff. Thus with the increase of temperature, the contribution of the 1st-order Zeeman
effect (which is temperature dependent and governed by Curie's law) arising from the J =! state
2
decreases while the contribution of 2nd order Zeeman effect from the J = ~ state increases. This
_ 2
is why, with the increase of temperature, J.leff does not change (Fig. 8.20.3.5) remarkably (ef for the d l _
octahedral systems, J.leff changes remarkably with temperature).
3.0
ry
9
Cu(lI) (d , Td , 2T2 ): Spin-orbit coupling
~
ai splitting of the ~2 state
ra
c
::.=- • Ground state (J = 1/2, g = 2) is
en
.0
2.0 magnetic i. e. contribution of 1st order
:f
ib
Zeeman effect
• Excited state (J = 3/2, g =0) is
\
yl
nonmagnetic (i.e. no 1st order Zeeman
r 1.738.M.
effect) producing only the 2nd order
m
Zeeman effect.
1.0
he
100 200 300
- - -..
~ T(K)
lc
Fig. 8.20.3.5 Variation of J.lobs with temperature for the tetrahedral Cu(II)-complexes.
ea
(D) Comparison of the magnetic behaviour of the octahedral t~g and ~g (I.s.) systems and tJ8
(e 4tt) tetrahedral system characterised by the ground state term 3T1(g) (L = 1, S = 1): The 3T1g level
th
of the octahedral complexes splits through the spin-orbit coupling into three levels characterised by J
= 0, 1, 2. Because of the negative correspondence between the t 2g and p levels in terms of the orbital
e/
i
angular momentum integrals, for t2 (less than half filled i. e. A = +ve), the ground state is J = 2 while
for 12; (more than half-filled i.e. A = -ve), the ground state is J = O.
t.m
i)
3T1g (t 2 == 3p(p4); 3TIg(t2~ == 3p(p2). (ef pn = p6-n, hole formalism rule)
Note:
i (less than half-filled)
e
(i) A = +ve for t2

er
A = -ve for t 2; (more than half-filled)

A = -ve for e ti (tetrahedral, more than half-filled).
4
H
• 3T1 term arising from tf'(Td ) and 3T1g term arising from low-spin er( 0h' t 2;) will undergo the
similar spin-orbit coupling splitting. But the J levels will be inverted for tf'(Td ) and d4 (low-spin
k
0h) compared to the J-Ievels arising from the cP-Oh configuration.

lic
i,
For, t2 ground level is J = 2; for t2;, ground level is J = 0; for e4 ti, ground level is J = O. This
can be realised in terms of the sign of A.
C
(ii) A in the expression of gJ can have the values in the range A = 1 (strong field limit) to A = 1.5 (weak
field limit).
... =_A+(2+A){J(J+1)+S(S+I)-L(L+l)} J~O

(111) gJ 2J (J + 1) ,
=-A + (2+ A) x J(J + 1) +(2+ A){S(S + 1) - L(L + I)} = (1- A) + (2 + A){S(S + 1) - L(L + I)}
2J(J +1) 2J(J +1) 2 2J(J +1)
Splitting by spin-orbit
coupling Splitting by magnetic
field
~ ,---A-----.
J=O
r----------r---- - - - - - - -----
I
I
I 2AA
ry
I
I
I AI..
I
ra
I
I
I
II J=1 " } 9J=A

-----~----,~~:--
ib
I __ -- - - - -
" II AI.. " 1 -"2

I I ----
yl
I I
I I
I II
I I AI..
m
I I
I I
I I
I II
he
II
,,
-------~~--------------------
(L = 1, S = 1) ,,
,,
,,
,,
lc AI..
,.----
ea
,
,
"---_-A-A--------l""---....,;;'~~::::-=
J=2
,...:-.::""
=
A
1--
2
th
0 _
e/
Fig. 8.20.3.6 Spin-orbit coupling splitting of the 3T1g term arising from the t~g configuration in an octahedral field.
t.m
(Inverted diagram for the low spin t~g and e4ti tetrahedral complexes)
From the expression of gJ in terms of y discussed earlier, the present expression in terms of A is
obtained by replacing y by -A. It may be noted that the above expression is not validfor J= 0 because
e
it makes g undefined. For J = 0, the relation is: g = -A + (2 + A)(L + 1) = 4 + A (for L = 1). Taking
er
1 1 1 1
A = 1 we get g = 5, 2" and 2" for J = 0, 1 and 2 respectively. Taking A = 1.5, we get g = 52"' "4 and
H
1
"4 for J = 0, 1, and 2 respectively.
k
Thus for K 3[Mn(CN)6] (low spin t1g ), the ground state (J = 0) is nonmagnetic (i.e. lacking in making
lic
any 1st order Zeeman effect contribution). In fact, at very low temperature (tending to 0 K), the tig
system tends to show the zero magnetic moment. The small residual paramagnetism is TIP (i.e. 2 nd order
C
Zeeman effect). However, with the increase of temperature, the population density at the higher J values
(= 1, 2) increases and f.leff tends to increase because, these higher J-states can show both the 1st order
and 2 nd order Zeeman effect. Here it is worth mentioning that for the t 2 system as in the octahedral i
complexes of V(III) (ground state, J = 2), even at low temperature f.lejJ retains the finite value because
of the 1st order Zeeman effect contribution from the J = 2 level. For the tetrahedral complexes of
Ni(II) (e 4 ti; ground state J = 0), at very low temperature, the population density at the J = 0 level
increases but this level cannot make any contribution to XM through the 1st order Zeeman effect; it
makes only a little contribution from the 2nd order Zeeman effect. At high temperature, higher mag-
netic J levels become populated and f.lejJ increases as in K 3 [Mn(CN)6].
Note: Kotani expressions for the other systems like cfl( 0h) and cf'(Td) having the 3TI term, tf( 0h) and
cf(Td ) having the 5T2 term, d' (Oh) and d3(Td ) having the 4TI term can be derived from the van-Vleck
l
equation as in the case of d ( 0h) and cf(Td ) complexes. These are not discussed here.
8.21 MAGNETIC PROPERTIES OFTHE SECOND AND THIRD TRANSITION SERIES

For the complexes of the 1st transition series, the observed magnetic moment is very close to the
ry
Jlspin-only value. It allows the prediction of the number of unpaired electrons. From this, the oxidation
state can be assigned. But, for the heavier transition metal ions, the process becomes complicated. In
ra
fact, interpretation of magnetic data of the heavier transition metal ions is complicated due to many
factors such as high spin-orbit coupling constant, orbital contribution, magnetic exchange inter-
ib
actions, formation of metal-metal bonds, inapplicability of the Hund's rule in some cases, etc.
yl
The heavier transition metal ions generally prefer to form the low-spin complexes. It is due to their
higher crystal field splitting power and lower pairing energy. The 4d and 5d orbitals are spatially larger
m
(cf. relativistic expansion, Vol. 1) than the 3d orbitals. This reduces the electron-electron repulsion in
the heavier congeners and consequently this reduces the pairing energy.
he
In general, the spin-orbit coupling constant (Ar) for the heavier transition metal ions (cf. Sec.8.13)
is large and the multiplet width (El , l+l) is generally larger than the thermal energy (kBT). Thus, the
following working formula is expected to be applicable. lc
ea
JlJ =gJ~l(l+l) B.M.
It may be noted that the same working formula is also applicable for the lanthanides. For the systems,
th
multiplet width =::: kBT, then the higher l-levels also contribute according to their Boltzmann distribution
population density (as in the case of SmIII and EU III ).
e/
For the A and E ground states, the magnetic moments do not vary remarkably with temperature.
This is also approximately true for the heavier transition series. But, for the T-ground state, the
t.m
magnetic moment depends strongly on the temperature. This strong temperature dependence for the
heavier transition metal ions (where kBT/'A is very small) is illustrated in Kotani plot (cf. Fig. 8.20.3.2).
Let us compare the magnetic properties of Mn(III), Ru(IV) and Os(IV) to illustrate the effect of
e
temperature on the magnetic moment.

er
Ground state No. of unpaired J..lspin J.lobs (H.M.)

term electrons
H
80 K 300 K
k
Mn(III) (1 2;): 3T1g 2 2.83 3.31 3.50

lic
(in [Mn(CN)6]3-
Ru(lV) (1 2;): 3T1g 2 2.83 1.63 2.65
C
(in [RuC1 6P-)

Os(IV) (1 2;): 3T1g 2 2.83 0.78 1.50
(in [OsC16]2-)
For Mn(III), Jlobs is slightly greater than the Jlspin value. This slight enhancement may be argued for
the orbital contribution. For the heavier congeners, the observed magnetic moment is significantly less
than the Jlspin value. Moreover, the temperature dependence of JJ.obs is more pronounced for the
heavier congeners. If we compare between Mn(lll) (3d member) and Os(IV) (5d member), the Jlobs
value deviates severely from the Jlspin value for Os(IV). The very low value of Jlobs for Os(IV) apparently
misguides us regarding its oxidation state. At room temperature, Jleff apparently corresponds to one
unpaired electron suggesting the +3 oxidation state of osmium i.e. t2i. This apparent confusing situ-
ation arises due to the very high spin-orbit coupling constant in Os(IV) compared to that in
Mn(III). To analyse the magnetic property arising from the 3T1g ground tenn, we are to consider the
spin-orbit coupling splitting of the 3T1g term (ef Figs. 8.21.1 and 8.20.3.6).
Splitting by magnetic
ry
Splitting by spin-orbit field
coupling ~
ra
~ ,,~:~:: 9=1-~
I ~~~::: }
ib
"""" J=2 2
///,,/ A'A '.
yl
------------~\~------------------------------
m
(L = 1, S = 1) \~"
\ "" A'A
"
he
\
\ "
\
\
"" "
\\ '----J-=-1--+----z...-....-....---_· _
\
\
\
\
lc
2A'A
ea
\
J=O
th
Fig.8.21.1 (cf Fig. 8.20.3.6): Spin-orbit coupling of the 3Ttg term arising from the t2~ configuration (more than half filled
i.e. A =-ve). (A = 1 for the strong field limit; (cf For the 3T1g term arising from the t2~ configuration (less than half-filled,
e/
i.e. A = +ve), the ground level is designated by J = 2).

i
Thus for the t2 configuration, the ground level (J =0) is nonmagnetic jl;ff = g J (J + I) =0 for J = 0) . (cf. 2
t.m
In fact, there is no contribution of the 1st order Zeeman effect from this level. Thus, at this level, it
should show the diamagnetism. However, it may show some residual paramagnetism (i.e. TIP) from the
2nd order Zeeman effect through the higher i-levels. With the increase of temperature, the population
density at the higher levels (i.e. J = 1,2) increases and such higher levels can contribute to the magnetic
e
moment from the 1st order Zeeman effect. For Mn(III) having relatively lower A value, the higher
er
magnetic levels are sufficiently populated even at room temperature to show the paramagnetism from
H
the 1st order Zeeman effect. However, if it is taken to very low temperature (say 0 K), then it will remain
predominantly in the diamagnetic level (J = 0) and Jlobs tends to be zero. For Os(IV), at room tempera-
ture, it mainly exists in the level J = 0 (which is diamagnetic) because of the much higher value of A.
k
This is why, Jlobs becomes so low. In fact, the observed magnetic moment arises from the levels accord-
lic
ing to their population density as in the case of Sm(III) or Eu(III). If the magnetic moment of Os(IV)
is measured at very high temperature (i.e. kBT) multiplet width), then it would behave like the Mn(III)
C
complexes of room temperature (ef at very lower temperature, the Mn(III) complexes will behave like
Os(IV) complexes of room temperature).
8.22 CHARACTERISTICS OFTHE SECOND ORDER ZEEMAN EFFECT CONTRIBUTING

TO MAGNETIC SUSCEPTIBILITY (cf. Sec. 8.17)
8.22.1 Characteristic Features of the 2nd Order Zeeman Effect Contributing to the
Magnetic Susceptibility
We have already discussed this aspect in Sec. 8.17. Here we shall discuss the characteristic features of
the 2nd order Zeeman effect.
(a) Conditions for the 2nd order Zeeman effect: Both the excited and ground state must have the
same spin multiplicity. The excited state must have both the orbital and spin degeneracy. These aspects
are discussed in detail in Sec. 8.17.
(b) Nature of temperature dependence: The first order Zeeman susceptibility follows the Curie's
law and it is inversely proportional to temperature (n. But, the 2nd order Zeeman susceptibility is
independent of temperature. This is why, the 2nd order Zeeman susceptibility is referred to as tempera-
ry
ture independent paramagnetism (TIP).
ra
The second order Zeeman effect actually involves the coupling between the ground state and
well separated excited state under the influence of an external magnetic field. Because of such
ib
coupling, some electron density is pushed into the excited state in presence of an external magnetic
field. As the excited state is significantly higher in energy compared to the ground state, the thermal
yl
population density at the excited level is almost zero and it does not change appreciably with tempera-
ture. This is why, it appears as temperature independent.
m
N 2A2 C
he
XM(totaI) -- XM(Ist order) + XM(2nd order) -- All TfJ + N A a -- -T + N A a
3k
B
lc
If the excited state is not far removed from the ground state, the effect of temperature on the
magnetic properties becomes complicated. It occurs so for Sm 3+ and Eu 3+ for a moderate value of
ea
temperature. For Sm3+ and Eu3+, the 2nd order Zeeman effect can only be considered as tempera-
ture independent at very low temperature where kBT is negligible with respect to the energy
th
difference between the ground state and excited state. It can be shown that if the energy difference
between the ground state and excited state is very small compared to the thermal energy (kBn, then the
e/
2nd order Zeeman effect introduces the temperature dependent paramagnetism.

Let us illustrate the 2nd order Zeeman effect for Sm(lll) where the multiplet width is comparable to
t.m
kBT. The 2nd order effect does not occurfor the interaction between the statesfor which the J value differs by
more than unity. For Sm(III), the ground state is characterised by J = 2 and the first and second excited
2
e
states are characterised by J = 2. and 2. respectively with A : : : 240 em-I. At oridinary temperature
er
· 2 2
(kBT::::: 200 em-i), all these three levels remain populated according to Boltzmann distribution law. All
H
these three states can contribute to the 1st order Zeeman effect according to their population densities.
The 2nd order effect also arises from these thermally populated states. f,'le state characterised by
k
J = 2. can participate in the 2nd order interaction with the J =~ state (i.e. lower state) as well as with
lic
2 2
the J ="29 state (i.e. higher state) i.e. the 2nd order effect originates from the interaction between the
C
5 7 7 9
J =-and J =- states and J =- and J =- states. Thus for Sm(III), at very low temperature, the
2 2 2 2
ground state (i.e. J = ~ ) is mainly populated and population density at the excited state (i.e. J = 2. ) can
2 2
be reasonably assumed to be zero. Under this condition, the second order Zeeman effect arises only
from the interaction between the ground state ( J = ~ ) and the first excited state ( J = 2. ) and this effect
2 2
may be considered to be temperature independent. It indicates that the contribution of the 2nd order
Zeeman effect depends on temperature for Sm(III). In fact, the 2nd order Zeeman effect becomes
temperature independent when the first excited lies far above the ground state (i.e. L!E kBT). »
Temperature dependence of the 2nd order Zeeman effect
~ = energy difference between the ground state and excited state which will be mixing with
the ground state in the presence of an external magnetic field.
ry
kBT = thermal energy.
ra
• If dE » kBT, it leads to the temperature independent paramagnetism (TIP).
• If ~ ~ kBT, it leads to the temperature dependent paramagnetism, as expected from Curie's
ib
equation. In such cases, both the ground state and excited state participate in both the 1st and
yl
2nd order effects.
m
(c) Magnitude of the contribution to XM from the 2nd order Zeeman effect: The second order
Zeeman susceptibility is inversely proportional to the energy difference (liE) between the interacting
he
levels i. e. ground level and excited level. This energy separation is really quite large and conse-
quently magnitude of the second order Zeeman susceptiblity is quite small. In fact, this contribution is
lc
only accountable only when there is no spin moment or very small spin moment.
(d) Field induced phenomenon: Like the diamagnetism, the paramagnetism arising from the 2nd
ea
order Zeeman effect only exists in presence of the externally applied magnetic field. Its magnitude is
of the same order of diamagnetism.
th
(e) 2nd order Zeeman effect for the d5 (h.s.), tJ6 (I.s.), tJO and d 10 systems: When the ground state
is diamagnetic (i.e. S = 0), the mixing of an excited state through the spin-orbit coupling cannot induce
e/
the paramagnetic susceptibility. It happens so for the low spin Co(lll) complexes (~g, IA Ig' diamagnetic
state). However, the 2nd order effect i.e. interaction between the IA Ig state and ITIg state (excited state
t.m
which is capable of making an orbital contribution) under the influence of an external magnetic field
can induce a paramagnetism for the low spin Co(III) complexes. For a high-spin d 5-system (e.g. Fe3+
and Mn 2+ complexes), the grond state is 6A Ig (~g ei, L = 0) having no orbital angular momentum. For
e
such a system, there is no excited state with the spin multiplicity 6. Consequently, the high spin
er
cP systems do not enjoy any 2nd order Zeeman effect. Because of the same ground, the tfJ, dID systems,
i.e. IAI(g) (L = 0, S = 0) do not enjoy the 2nd order Zeeman effect.
H
It may be mentioned that the tJO-systems (e.g. CrO~-, MnOi) fail to enjoy the 2nd order effect in
terms of the ionic model (i. e. CFT) but in terms of the covalent model, such systems can experience the
k
2nd order effect. This aspect has been discussed in Sec. 8.22.2.
lic
Different names of the 2nd order Zeeman Susceptibility

C
Temperature independent paramagnetism (TIP), Van-Vleck high frequency paramagnetism, residual

paramagnetism, etc. are the different names.
Here it should be mentioned that the term TIP is applicable only when the energy difference
between the interacting energy levels (i.e. ground level and first excited level) is much higher
than kBT, Le. population density at the excited level is almost zero within the temperature range
of study.
(f) Magnitude of susceptibility due to 2nd order Zeeman effect for the A and E ground state
terms:
(i) A 2(g) ground state interacting with the T2(g) excited state:
8N Ap2
10Dq
(ii) E(g) ground state interacting with the T 2(g) excited state:
ry
_ 4N A p2 4N A p2
ra
XM (2nd order) - E(E) - E(T
2
) 10Dq
ib
It may be noted that for the ground state 6A 1(g) term (for high spin d5 ) and the lA IC~) term (for cP, d lO ),
there is no contribution of XM(2nd order).
yl
In general, we can write:
m
Taking orbital reduction
he
factor unity
4N A p2
E ground state term: XA-f(TIP)(E) = lc
10Dq
ea
(iii) lA 1g ground state (t~g) in low spin Co (III), Fe (II), etc. systenzs: The IA lg ground state interacts
with the 1T 1g excited state.
th
_ 8NAP2
e/
XM (2nd order) - 10Dq

t.m
In the above expressions, electron delocalisation has been ignored i.e. orbital reduction factor (k) has
been taken to be unity.
8.22.2 Some Representative Examples Having XM(TIP) or XM(2nd

e
order)
er
(i) Low-spin Co(III) complexes (t 2:, lA 1g ): There is no contribution of the 1st order Zeeman effect
H
from the lA Ig ground term (J = S = 0). The magnitude of XM(TIP) is 8N AP2 (taking orbital reduction
10Dq
factor k = I i.e. electron delocalisation is ignored). The energy difference (~E) between the IA Ig
k
(ground state) and 1T 1g (I st excited state) can be obtained from the electronic spectra. From this
lic
~ value 10Dq can be estimated (see Chapter 7). For [Co(NH 3)6]3+, ~E ::::: 21,000 cm- l , it leads to
6
XM(TIP)::::: 135 x 10- (CGS unit) which is larger than the experimental value. This discrepancy can
C
be removed by introducing the orbital reduction factor. For the higher ~ values, i.e. 10Dq
values, XM(TIP) becomes less. For the low-spin Co(III) complexes, XM(TIP) has been found in the
order of (50 - 100) x 10-6 mol- l cm 3 (CGS unit).
XM(TIP) per mole J.leff(TIP)
(CGS unit) (300 K) (B.M.) (300 K)

[Co(NH 3 )6]3+: 90 x 10-6 0.45
[Rh(NH 3)6]3+: 50 X 10-6 0.35
The relatively smaller values for the Rh(III) complexes is due to the higher 10Dq value. The
second order Zeeman effect in such cases arises due to the mixing of the lA 19 state (ground state)
and excited state ITIg and the energy difference between the IA lg state and ITIg state is approxi-
mately 10Dq - 4B. This energy difference may be obtained from their electronic spect~a.
Note: Considering the orbital reduction factor k i.e. electron delocalisation, we can write:
8N A~2k2
ry
XM(TIP) = 10Dq
ra
From the experimental value of XM(TIP), k can be calculated.
(ii) High spin dS-octahedral complexes (6A 1g ): The ground state is 6A Ig and there is no excited state
ib
having the same spin multiplicity. This is why, both the spin-orbit coupling effect and second
yl
order effect will remain absent. The ground state ~g e~ cannot also make any orbital contribution.
This is why, for such complexes, J.!obs is very close to J.!spin.
m
K2S04·MnS04·6H20: J.!obs = 5.90 B.M. and J.!s = 5.91 B.M.
(iii) Low-spin Co(II) complexes (/ 2: e:,2Eg ): There is only one unpaired electron contributing Jlspin =
he
1.73 B.M. (= XM = 1250 X 10-6 in CGS unit, at room temperature). The XM(TIP) is given by
4NA~2/IODq and for [CO(N0 2)6]4- (IODq::::: 14000 cm- I ), it becomes 75 x 10-6 (in CGS unit). Thus
lc
in [CO(N0 2)6]4-, XM(TIP) contributes about 5% to the total magnetic susceptibility observed at room
temperature. Here it may be considered that at the lower temperature, Curie law component
ea
is more important, and XM(TIP) is relatively less important.
th
XM(totaI) = ~ + XM (T1P) '" ~ (at the relatively lower tempeture)

e/
Curie component
(iv) Ni(II) octahedral Complexes (/2: e;,

3A 2g ): There are only two unpaired electrons contributing
t.m
6
J.!spin = 2.83 B.M. (= XM = 3,340 X 10- in CGS unit, at room temperature). The magnitude of
XM(TIP) is given by 8NA~2/10Dq (ignoring the electron delocalisation) and by considering the 10Dq
values of the common octahedral complexes of Ni(II), XM(TIP) becomes about 250 xlO-6 (in CGS
e
unit). Thus, XM(TIP) is about 8% of XM(spin) and thus XM(TIP) is quite accountable.
(v) Octahedral complexes of Cu(II) (12~ ei,
2Eg ): The one unpaired electron contributes with
er
J.!spin = 1.73 B.M. and XM(spin) = 1250 X 10-6 (in CGS unit). By considering the 10Dq values of the
octahedral complexes of Cu(II), 4NA~2/1 ODq (without considering the electron delocalisation)
H
leads to XM(TIP) = (80 - 90) x 10-6 (in CGS unit). Thus XM(TIP) is about 7% of XM(spin).
(vi) XM(TIP) for the tetrahedral complexes with the ground A and E terms: Here it should be
k
mentioned that XM(TIP) is inversely proportional to 10Dq. 10Dq values for the tetrahedral com-
lic
plexes are relatively smaller compared to those of the octahedral complexes. Thus the magnitude
of XM(TIP) is relatively more important in the tetrahedral complexes compar~d to that of the
C
octahedral complexes.
The relevant systems are:
d I (2E, V4+), d 6CSE, Fe 2+), d7(4A 2, C0 2+)
XM(TIP) is quite important for the d (J.!s= 1.73 B.M.) and ~ (J.!s = 3.87 B.M.) octahedral complexes
l
where XM(spin) is not very high.

It has been found that in [VCI4], XM(TIP) contributes about 10% to the total susceptibility at roon1
temperature.
In the tetrahedral Co(II) complexes, by considering the common 10Dq values, XM(TIP) has been
found 650 x 10-6 (in CGS unit) without considering the electron delocalisation factor. This fairly
high XM(TIP) value is quite important. There are three unpaired electrons contributing XM(spin) =
6,260 x 10-6 (in cas unit). It indicates that XM(TIP) is about 6% of XM(spin).
XM(TIP) for the A g ground term: The systems are: high-spin d 3 -octahedral complexes (4A 2g ;
Cr3+, Mn4+), low-spin d 6-octahedral complexes eA 3 3 8
1g ; C0 +, Rh +), d -octahedral complexes
(3A 2g ; Ni2+).
ry
Among these systems, XM(TIP) is only accountable with respect to XM(spin) for the d 8-octahedral
complexes and for the d 6-octahedral low-spin complexes (where XM(spin) is zero).
ra
4 3
XM(TIP) for the E g ground term: The systems are: high-spin d -Oh (SE g ; Cr2+, Mn +), low-spin
2 9 2
d' -Oh (2 E g ; C0 +), d -Oh (2 E g ; Cu +). XM(TIP) is only accountable with respect to XM(spin) for the
ib
2Eg term.
yl
(vii) 2nd order Zeeman effect in Sm(III) and Eu(III): XM(2nd order) is inversely proportional to the
m
energy separation between the ground state and excited state. This energy separation is quite large
for the lanthanides except for Sm(III) and Eu(III). Thus XM(2nd order) is quite negligible for all other
he
lanthanides compared to XM(1st order) that mainly arises from the ground J-Ievel. In Sm(III) and
Eu(III), the said energy separation is comparable to kBT and thus the excited states also contribute
lc
to XM(1st order) according to their Boltzmann population density. These aspects have been already
discussed (Sec. 8.19.1).
ea
The above discussion indicates that the XM(2nd order) is negligible for the other lanthanides but it is
relatively important for Sm(III) and Eu(III) where I1EJ. J+l :::: kBT. Thus for Sm(III) and Eu(III)
th
both 1st order and 2nd order Zeeman effect contribute to the total XM•
• Sm(III) (cf. Sec. 8.19.1): The ground state is 6Hs/2 and the first and second excited states are: 6H7/2
e/
and 6H912 respectively. For J = 5/2 (ground state), the second order effect will arise for the coupling
between the J = 5/2 and J = 7/2 states. However, there will be a certain population density at J =
t.m
7/2 (i.e. 1st excited state). For J/2, the 2nd order effect will arise due to coupling with J = 5/2 as
well as with J = 9/2. The population density at J = 7/2 depends on temperature. Thus the net 2nd
5 7 7 9
e
order effects due to the interactions between the states J = 2" and 2"; and J = 2" and 2"
er
show a dependence on temperature i.e. here the 2nd order effect is not the case of TIP.
H
• For J = 5/2, the second order interaction arises for the interaction with J = 7/2 i.e. interaction
=-7 5
k
between J and -.
2 2
lic
7 5
(ii) For J = 712, there two sources of 2 nd order effect i. e. interaction between J = 2" and 2";
C
7 9
J =- and -.
2 2
• Eu(III) (cf. Sec. 8.19.1): The ground state 7Fo (i.e. J = 0) cannot produce any 1st order Zeeman
effect. The first excited state 7F 1 (i. e. J = 1) can contribute to XM(1st order) according to its population
density. At very low temperature, where the ground level (i.e. J =0) is mostly populated, there will
no contribution to XM(total) from the 1st order Zeeman effect and the small value of XM is due to the
2nd order effect from the coupling between J = 0 and J = 1. In fact, at very low temperature, the
residual paramagnetism noted is due to the 2nd order effect and it is temperature independent for
the condition I1EO,1 » kBT. But at a relatively higher temperature, the population density at J = 1
becomes quite appreciable and this level can show the 1st order Zeeman effect and also the 2nd
order effect due to the interaction with the states J = 0 and J = 2.
(viii) TIP of K[Mn04] and K2[Cr04]: Mn(VII) and Cr(VI) represent the cfJ system (i.e. S = 0, L = 0)
and they are expected not to show any paramagnetism. However, they show a very small
parmagnetism. In terms of ionic models (i.e. eFT), a cfJ system cannot experience any paramag-
netism from both the 1st order and 2nd order Zeeman effects. But if [Mn04]- and [Cr04]2- are
ry
treated as the covalent moieties then in terms of MOT (cf Figs. 7.21.6, 7), the ground state is
diamagnetic but the excited states are paramgnetic. The 2nd order Zeeman effect producing an
ra
interaction between the diamagnetic ground state and paramagnetic excited state gives the small
paramagnetism i.e. TIP.
ib
8.23 CONSEQUENCE OF ELECTRON DELOCALISATION ON MAGNETIC PROPERTIES:
yl
EVALUATION OF DELOCALISATION FACTOR, i.e. ORBITAL REDUCTION FACTOR
m
Very often, due to the overlap between the metal and ligand orbitals, the electron density in the metal
orbitals is reduced through the delocalisation. Consequently, the orbital angular momentum is reduced
he
and it is measured by a factor k which is called the delocalisation factor or orbital reduction factor.
It means that the electron spends a fraction k of its total time on the metal centre. Due to this delocalisation,
the amount of orbital angular momentum is kL instead of L. lc
The value k = 1 indicates no delocalisation and the value k ( 1 indicates delocalisation. Thus the
ea
magnitude of k gives the measure of electron delocalisation. Electron delocalisation through the
n-bonding is quite important. In the octahedral complexes, the t2g electrons and in the tetrahedral
th
complexes, the e-electrons will participate in n-bonding giving rise to delocalisation. Here it may be
mentioned that the metal-ligand a-bonding can also lead to electron delocalisation. It may be pointed
e/
out that the delocalisation factor may be comparad with the nephelauxetic effect.
t.m
By taking into the consideration of k, the total magnetic moment arising from both the 1st order and
2nd order Zeeman effects can be expressed as follows:
8k A] 8k N A~2
2 2
For Arterms: XM(A 2 ) = XM(spin-only) [ 1- lODq + lODq
e
er
2
4k2A] 4k N ~2
For Erterms: XM(E) = XM(spin-only) [ 1- lODq + IOD~ .
H
From the measurement of magnetic susceptibility, we can calculate the k value. It is illustrated in the
k
following examples.
(a) K 2Ba[Co(N02)6] (/2: e:,
2Eg ): At 300 K, XM = 1370 X 10-6 (in CGS unit), taking NA f3 2 =
lic
0.261 cm- I erg gauss-2 mol- I (cf f3 = 9.274 X 10-21 erg gauss-I; 1 cm -I = 2.86 cal mol-I; 1 erg = 2.39
x 1O-ll kcal), 10Dq = 14,000 cm- I ,
C
_ 4k N A~
2 2 2
4k x 0.261 2 6 ( . . )
XM (2nd order) - IODq 14,000 = 74.6k X 10- per mole III CGS umt
A = -515 cm- I , XM(spin) = 1250 X 10-6 (in CGS unit).

It leads to:
2
J
1370 X 10-6 = 1250 X 10-6 (1- 4k x -515 + 74.6k 2 X 10-6
14,000
or, 1370 = 1250(1 + 0.15 k 2 ) + 74.6k2
Solution of the above equation leads to k =:: 0.70. It indicates the sufficient delocalisation of electron.
(b) [Ni(OH2 )6]S04 (/ 2: ei, 3A 2g ): The results are:

= 4340 X 10-6 (in COS unit), at 300 K.
XM(totaI)
10Dq = 8,900 em-I, A = -315 em-I, XM(spin) = 3333 X 10-6 (COS unit).
= SN A~2k2 S xO.261 x e = 234.6e x 10- 6 (CGS unit)

XM(2 nd order) 10 Dq 8,900
ry
It leads to:
ra
4340 X10-6 = 3333 X10-6 (1- Sx8,900 J+
-315k
2
234.6k 2 X10-6
ib
= 3333( 1 + 0.28k2) + 234.6k2
yl
or, 4340
Solution of the above equation leads to k = 0.93. It indicates that the delocalisation is quite small.
m
(c) Cs 2 [CoCI4 ] (e 4/ 23, 4A 2 ): XM(totaI) = 9,250 X 10-6 (in COS unit) at 300 K.
he
10Dq = 3,200 em-I; A = -172 em-I; XM(spin) = 6,250 X 10-6 (CGS unit).
_ 8N A~2k2 S x 0.261 x e =653 x ]0-6 (CGS unit)

lc
XM (2nd order) - 10Dq 3,200
ea
It leads to:
th
2
9,250 X10-6 = 6,250 X10-6 (1- 8k x -172 + 653 X10-6 J
3,200
e/
or, 9,250 = 6,250(1 + 0.43k2) + 653

t.m
It leads to: k = 0.95, i.e. delocalisation is negligible.

(d) [Cu(OH2)6]2+ (/2~ ei, 2E g ): The results are: 10Dq = 12, 000 em-I; A = -830 em-I, XM(spin) = 1250
x 10-6 (COS unit); XM(2nd order) = 85 x 10-6 (COS unit), XM(total) = 1520 x 10-6 (CGS unit). It leads to:
e
(1- 2
er
1520xl0-6 =1250XI0-6 4k X-S30J+85k 2 xl0-6

12000
H
or, 1520 = 1250(1 + 0.28k 2 ) + 85k 2 ; or k :::: 0.8

k
i.e. delocalisation is about 20%.

lic
(Note: Evaluation k in this method is not very much accurate because it depends on the accuracy of
determination of magnetic susceptibility. Very often, determination of the magnetic susceptibility value
C
is not very much accurate.)

Qualitative interpretation of k-value: Table 8.23.1 records the k-values of some complexes. These
k values are evaluated from the magnetic susceptibility determination. Electron delocalisation in
[Ni(PPh3)2X2] is more than that in [NiX 4 ]2- (X = CI, Br). It is also reflected in the lower k values for
[Ni(PPh3)2X2]. For the cyanido complexes experiencing the metal to ligand electron movement (property
of a n acid ligand), the reduced values of k are quite reasonable. But, for the bpy and phen complexes,
the delocalisation factor unity is quite unexpected because hpy and phen can also act as the n-acid
ligands. Similarly, in the aqua complexes where there is no efficient n-bonding, the low values of k are
not expected. Thus the k values obtained from the XM data are not very much reliable.
Table 8.23.1 Orbital reduction factor (k) in some complexes

Complex k
[Cr(OH 2)6]CI 3 0.80

[Ti(OH 2)6](S04)1.5 0.80
ry
[Cu(OH 2)6]2+ 0.80
[Ni(OH 2)6]S04 0.93
ra
K 3[Fe(CN)6] 0.80
1.0
ib
[Fe(bpYh](S04)1.5
[Fe(phen)3](SO4) 1.5 1.0
yl
K4[Mn(CN)6] . 3H 20 0.75
m
Cs 2[CoCI 4] 0.95
(Et4Nh[NiCI 4] 1.00
he
[Ni(PPh3)2X2] (X = CI, Br) 0.55
lc
8.24 MAGNETIC PROPERTIES FOR THE THERMAL EQUILIBRIUM BETWEEN THE HIGH
ea
SPIN AND LOW SPIN STATES INTHE CROSS-OVER REGION (ct. Sec. 3.8.2)
8.24.1 Condition for Thermal Equilibrium between the High Spin State and Low Spin
th
State of the Octahedral Complexes (ct. Sec. 3.8.2)

cr,
e/
It has been already illustrated (Sec. 3.8.2) that for the d 5 , cf' and d 7 systems, the high spin ~ low
spin equilibrium, may prevail under the condition, 10Dq ::::: P. This 10Dq value is called the critical
t.m
lODq value. In fact, we have the conditions:

Low spin: 10Dq ) P; High spin: 10Dq ( P ; Spin isomerism: 10Dq::::: P.
(a) Conditions favouring the low-spin state: Obviously, the higher oxidation state and heavier
transition metal ions showing the higher 10Dq values will favour the low-spin state. Similarly, the
e
strong field ligands will favour the low-spin state. The ligands showing the high nephelauxetic effect
er
(i. e. reduction in Racah parameter B) will reduce the pairing energy to favour the low spin state.
The critical 10Dq value (leading to the spin state isomerism) is also described as the high spin-low
H
spin cross-over point. In the cross-over region, the energy difference between the two spin states lies
in the thermal energy range (kBD, i. e. dE = Eh.s . -- El. s . ::::: kBT. Consequently, population density at the
k
two states is controlled by Boltzmann distribution. If the low spin state is the ground state (i.e. of higher
lic
cfse), then with the increase of temperature the population density in the excited state (i.e. high spin
state) increases.
C
Critical lODq (= P) values for the following first transition metal 'ions are given below.
d 4 : 23,500 cm- l (Cr2+), 28,000 cm- l (Mn 3+) )
tF: 25,500 cm- 1 (Mn 2+), 30,000 cm- 1 (Fe3+) (cf Table 3.8.1.2)
cf': 21,000 cm- l (C0 3+), 17,600 cm- l (Fe 2+)
d 7 : 19,500 cm- l (C0 2+).
(b) Cross-over point in terms of potential energy curves of high-spin and low-spin complexes:
In the high-spin complexes, electron density in the eg-Ievel is relatively more. Consequently, the
metal-ligand distance in the high-spin complex is relatively longer i.e. M-L (high-spin) ) M-L
(low-spin) where M-L indicates the metal-ligand bond length. In terms of stretching frequency:
(1.s.) ) V M - L (h.s.).
V M- L
ry
\--+------------1 High-spin
5 4 ~
(e.g. T2g1 t2g eg)
ra
ib
yl
m
he
~ ~J
r------I
lc
L -_-_-_ -_-_ !lEo'" k B T (Thermal spin cross-over)
ea
I
I
I
th
e/
--------.~ Nuclear coordinate (i.e. bond length), r

t.m
Fig. 8.24.1.1 Potential energy curves for the high-spin and low-spin complexes at the crossover point.
Note: Thermal spin crossover under the condition: ~Eo ~ kBT.

Fig. 8.24.1.1 shows the representative potential wells of the high-spin and low-spin complexes.
e
Crossover point leading to the spin state isomerism arises when the difference (~o) in zero-point
er
energies of the two states is in the order of kBT, i.e. ~Eo ~ kBT. This condition is attained when the
pairing energy is close to 10Dq.
H
For such a thermal spin cross-over, properties (spectra, magnetic moment, reactivity, etc.) depend
on temperature because the situation allows the thremally induced spin transitions.
k
(c) Condition for cross-over point leading to the spin state isomerism in terms of Tanabe-
Sugano diagrams (cf. Sec. 3.8): From the Tanabe-Sugano diagrams (ef Figs. 7.13.2.1) for the d4 - d7
lic
configurations, the cross-over point (i.e. the point at which energies of the high-spin and low-spin states
are the same) exists at the following 1ODq/B values:
C
d ll : d4 d5 d6 d7
(1 ODq/B)cross-over : 27.0 28.0 20.0 22.0
10Dq (IODqJ
High-spin Complex: -B- < -B- • Reduction in the B value (i.e. good nephalauxatic
cross-over effect) favours the spin pairing
• Reduction in the B value reduces the pairing
·
LOW-SPill 10Dq
Complex: - - > (IODqJ
-- energy to favour the sp~n pairing.
B B cross-over
The Racah parameter B does not change remarkably for the different dn-configurations (at least for
the first transition series metal ions). Thus, it is evident that at the low lODq value, the d 6 configuration
can adopt the low-spin configuration while the tJS configuration requires the very high lODq value
for spin pairing to produce the low-spin complex. Thus the ease of spin pairing follows the sequence:
d6 ) d7 ) d4 ) d5
In fact, the cf configuration of Co(lll) can easily form the low spin (t2~ e~) complexes. For Co(III),
ry
only two high-spin (12: e;) complexes are known. These are: [CoF6]3- and [CoF3(OH2)3]. It may be
noted that on the other hand, thousands of low spin complexes (t2~) of Co(lll) are known. For Fe(lll)
ra
(~ system), most' of the complexes are the high spin complexes and only for the very strong field
ligands, Fe(lll) can form the low-spin complexes like [Fe(CN)6]3-, [Fe(phen)3]3+, [Fe(bpY)3]3+. Mn(lll)
ib
(cJ4) also shows a preference for the high-spin complexes and it can form the low-spin complexes with
yl
the very strong field ligands like the CN-. Thus the experimental evidences also support the ease of low-
spin complex formation in the order: d 6 ) d 7 ) d 4 ) d 5 •
m
(d) Interpretation of the ease of spin pairing in terms of exchange energy (cf. Sec. 3.7): The
exchange energy (Eex ) is proportional to n(n - 1)/2 where n = number of unpaired electrons with the
he
parallel spin. Thus on spin-pairing, there is a loss of exchange energy (~ex) (cf. Sec. 3.7)
d" Configuration lc
Loss of exchange energy;
AEex (h.s. to l.s.)
Gain of cfse (h.s. to l.s.)
(ignoring the pairing energy)
ea
cr (h.s.: tig e~; 1 x lODq
I.s.: fig e~)
th
d 5 (h.s.: ~g e;; 2 x IODq

e/
I.s.: ~g. e~)

tJ6 (h.s.: t~g e;; 2 x IODq
t.m
I.s.: ~g e~)
tf! (h.s.: ~g e;; 1 x IODq
I.s.: ~g ei)
e
er
Kex is the proportionality constant i.e. Eex = Kex'l(n - 1)/2, Kex remains more or less the same for a
particular oxidation state. In the above calculation, it has been assumed that the energy difference
H
between the t2g and eg levels does not prevent the electron exchange process (cf. Sec. 3.7 for more details).
Thus, per gain of lODq cfse, the loss of exchange energy is: 3Kex for d 4 and d 5 , 2Kex for d 6 and d 7
k
systems. Thus, in terms of loss of pairing energy, the ease of spin pairing follows the sequence:
lic
d 6, d 7 ) d 4, d 5
C
Spin isomerism in nonoctahedral complexes (ct. Sec. 8.25)
In the tetrahedral complexes, the 10Dq value is about .i th of that in the octahedral complexes.
9
Consequently, in the tetrahedral geometries, the condition P ) lODq is generally maintained i.e.
most of the tetrahedral complexes are in high-spin state. The condition, 1ODq ~ P for the spin
isomerism is not generally attained in the tetrahedral complexes. Square planar complexes are
generally the low-spin complexes. The condition for spin isomerism is not attained generally in
the square planar complexes (cf. Sec. 8.25).
(e) Importance of nephelauxetic effect to favour the spin pairing: Strong field ligands producing
the high crystal field splitting will favour the spin pairing. Sometimes, the fairly weak field ligands
showing a pronounced nephelauxetic effect (i.e. high electron delocalisation) may favour the spin
pairing. This may lead to the situation of spin-state isomerism. This is illustrated for the Fe(lll) complexes.
P (for free Fe3+ ion) = 30,000 cm- 1, 10Dq for [Fe(OH 2)6]3+ = 14,000 cm- 1,
ry
10Dq for [Fe(dtc)3] = 15,500 to 18,000 cm- 1 (dtc = disubstituted dithiocarbamate)
Considering the pairing energy (P) as 30,000 cm- 1, both [Fe(OH 2)6]3+ and [Fe(dtc)3] are expected to
ra
have the high-spin configuration (t2~ e;,
P ) 1ODq). The [Fe(OH 2)6]3+ complex is having the high-spin
ib
configuration (supported by the magnetic moment data, J..l ::::: 5.9 B.M.). But the anomalous magnetic
moment of [Fe(dtc)]3 indicates the temperature dependent high spin ~ low spin equilibrium. This spin
yl
state isomerism is possible because in the complex, [Fe(dtc)3]' the extensive electron delocalisation
in the ligand orbitals reduces B significantly. Consequently, the (1 ODqIB)cross-over point (cf Tanabe-
m
Sugano diagram) is attained for the smaller 10Dq value. In other words, reduction in B lowers the
he
pairing energy. It has been estimated that in [Fe(dtc)3]' the B value is reduced to about 50% of the B
value of the free ion. It makes the paring energy in [Fe(dtc)3] in the range of 15,000 cm- 1 which is close
to the 10Dq value of the complex. It allows the spin state equilibrium.
lc
Here it is worth mentioning that because of the pronounced nephelauxetic effect shown by the sulfur
ea
donor ligands, having the vacant d-orbitals to receive the electron cloud from the metal d-orbitals
through the 1t-bonding, the pairing energy is lowered significantly and it allows the attainment of square
th
planar geometry in Ni(II).

e/
8.24.2 Effect of Pressure on Spin-State Isomerism

The h.s. ~ l.s. equilibrium is temperature dependent because of the possibility of thermally induced
t.m
spin transition. This aspect has been already discussed. The position of the equilibrium is also pressure
dependent.
The metal-ligand bond distance in the low-spin isomer is generally shorter than that in the corre-
e
sponding high spin isomer. It happens so because of the reduced electron density in the eg orbitals of
er
the low-spin complex. Thus the molar volume (VM) of the low-spin complex is less than that of its
high-spin isomer. Consequently, an increase in pressure will shift the equilibrium, h.s. ~ l.s. towards
H
the low-spin isomer having the lower molar volume. In fact, it has been noted that the magnetic
moment of [Fe(dtc)3] (dissolved in CHCI 3) decreases with the increase of pressure from 1000 atm
k
to 3000 atm. The magnetic moment of the low spin isomer (t2~ 2T2g , one unpaired electron) is less than
lic
that of the high spin isomer (t2~ e~, 6A 1g , 5 unpaired electrons). It explains the variation of magnetic
moment with the increase of pressure.
C
8.24.3 Anomalous Magnetic Properties due to Spin-state Isomerism in the Octahedral

Complexes (cf. Sec. 3.8)
In the octahedral complexes, the spin state isomerism arises in the cases given in Table 8.24.3.1.
For the equilibrium, l.s. ~ h.s., the resultant XM and J..l can be expressed as follows:
K = [h.s.] = _a_
l.s. ~ h.s.; eq [l.s.] (1 - a)
Table 8.24.3.1 Cases of spin state isomerism in the octahedral complexes
d" l.s. ~ h.s. J.ls (in H.M.) Examples

h.s. l.s.
er i
3T1g(t 2 e~) ~ 5Eit2~ ei) 4.90 2.83 Cr2+, Mn 3+
ry
d5 2T2g(t2~ e~) ~ 6A Ig(t2~ e;) 5.92 1.73 Mn 2+, Fe3+
ra
tf6 IAlit2~ e~) ~ 5T2g (t2i e;) 4.90 0 Fe 2+, Co 3+
ib
d7 2Eg(t2~ ei) ~ 4Tlit2~ e;) 3.87 1.73 Co 2+
yl
XM(obs) = aXM(h.s.) + (I - a)XM(l.s.); a = mole faction of the h.s. isomer.
J.!~bs = aJ.!1.s. + (1 - a)J.!T.s.
m
= aJ.!1.s. + J.!T.s. - aJ.!T.s.
he
= a(J.!1.s. - J.!T.s) + J.!T.s,
2 2
a = Ilobs - Ill. s.
lc
or, 2 2
Ilh.s. - Ill. s.
ea
2 2 2 2
1- a = 1_ Ilobs - Ill. s . Ilh.s. - Ilobs
and 2 2 2 2
th
Il h.s. - Ill.s. Il h.s. - IlI. s.
=~= (~~bS -~~s.)

e/
K
eq 1- a (2 2)
t.m
Ilh.s. - Ilobs
Thus from the knowledge of J.!h.s. and J.!l.s. and the experimental value of J.!obs (at a particular temperature),
the equilibrium constant can be evaluated. From the knowledge of thermodynamics, we can write:
~SO Mio
e
InK = - - - - -
eq R RT
er
1 A TJO •
From the plot of In K eq VS. T' LMl-- can be obtaIned from the slope and then by using the value of
H
MfJ in the above equation, ~SO can be calculated.

In the case of spin-state isomerism, energy difference between the two spin states is in the order of
k
kBT. Consequently, contribution of the two states to the total magnetic susceptibility depends on their
lic
population densities determined by Boltzmann distribution.

(A) Quantitative treatment for XM in the case of d 5 and d 6 systems experiencing the spin state
C
isomerism: In the case of d 5 (6A}g and 2T2g) and ~ (5T2g and IA 1g), the spin-orbit coupling integrals for
the interaction between the two isomeric spin states is zero because of the involvement of the A 19 term
(L = 0) in each case (i.e. 6A 19 for the high spin d5 i.e. t2~ e; and lA 19 for the low-spin tJ6 i.e. t2~)' It
indicates that there is no spin-orbit coupling interaction between the two spin states. In such cases,
the observed XM is the population weighted average of the magnetic susceptibilities of the two
isomeric states. It is given by: "
(2S 1 +l)XM(J) + (2S 2 +l)X M(II)exp(-y)

XM(obs) = (2S1 + 1) + (2S2 + 1)exp(-y)
2S 1 + 1 = spin multiplicity of the spin state (I)

2S2 + 1 = spin multiplicity of the spin state (II).
XM(I) = Molar susceptibility of the spin state (I)
XM(II) = Molar susceptibility of the spin state (II).
E(I) = energy of the spin state (I), E(l1) = energy of the spin state (II).
ry
~ E(II) - E(I)
ra
y=-=
kBT kBT
ib
The observed relation can be obtained as follows:
XM(obs) = aIXM(I) + aIIXM(II)
yl
aI and an denote the mole fractions of the spin states I and II having the molar susceptibilities XM(I)
m
and XM(II) respectively.
he
lc
ea
th
(2S 1 + 1) ex p[- E(I)]

kBT
e/
~I = -(2-S--+-I)-e-xp~[~_-E-(I-)-=-]-+-(2=-S-2-+-1-=)e-x-p[=---E-(-1I---=")]
t.m
1
'. kBT kBT
(2S1 + I)
r
e
. obtained by mUltiPIYingexp[ E(]l ]With the
E(ll~:/(]l numera~:~
er
(2S1 + 1) +(2S 2 + l)exp [ -{ } both denominator and

H
k
(2S 1 + 1) + (2S2 + l)exp( -y)

lic
C
(2S 1 +1)
all =1-a 1 = 1 - - - - - - - - - -
(2S 1 + 1)+(2S2 + l)exp(-y)
(2S 2 + 1)exp( -y)

(2S 1 +1)+(2S2 +l)exp(-y)
(2S 1 +1)X M(I) +(2S2 + l)X M(II)exp(-y)

XM(obs) -a X +a X - ---- ---------
- I M(I) II M(II) - (2S +1)+(2S +l)exp(-y)
1 2
(i) gradual transformation into the h.s. state; (ii) abrupt transformation, (iii) two step transformation,
(iv) incomplete transformation suggesting that all the molecules cannot be thermally excited to
higher energy states and it is also expected from the Boltzmann distribution function, (v) trans-
formation curve with a hysteresis loop - indicating the structural phase change during the spin
state change.
ry
1.0 ------------:~~.------------
/,'" /'7('
1.0 --~b~:~ --;,-r----7j5,~;~t~p
ra
I ,
transition , I
transition~: ~ +
, ~'
ib
,-
"--Incomplete : :~Transition
j ~_.k transition I : with a hysteresis
yl
+: loop
Gradual~
: ~,
m
transition " 7 , I
/ , ,
I I
he
.,/-
r",/'
----+ Temp (T K)
----+ Temp (T K)
(a) lc (b)
ea
Fig. 8.24.4.1 Different types of spin transition curves for the transformation of the low spin isomer into the high spin
isomer with the increase of temperature.
th
8.24.5 Examples Illustrating the Magnetic Properties of Complexes showing the Spin
State Isomerism in the Octahedral Complexes (ct. Sec. 3.8.2)
e/
(i) Fe(II) (d 6 ) complexes: The complexes like [Fe(NCS)2(phen)2], [Fe(NCSe)2(phen)2]'

t.m
[Fe(NCSe)2(phen)2] experience a spin state isomerism controlled thermally.
l.s.(t~g, 'A,g) ~ h.s.(tige~, 5T2g )

e
er
H
Slope=- 512
k
lic
P = 10Dqo
C
High-spin state
Region of critical 10Dqo
(Stable)
and region of thermal
equilibrium
Low-spin state
(Stable)
----.~ ~o
I.
Fig.8.24.5.1 Qualitative representation of variation of energies of 5T2g (i.e. t2~ e<~, h.s.) and IA lg (i.e. t2~ e~, I.s.) terms
arising froln the [f6-octahedral complexes (see Fig. 3.8.2.1 and Sec. 3.8.2).
e.
Here the high spin state isomer is of higher energy and with the increase of temperature, the population
density in the high spin state increases (cf Fig. 8.24.4.1). The low spin isomer having no unpaired
electron possesses only a negligible amount of paramagnetism called TIP while the high spin isomer
possesses a high magnetic moment (4 unpaired electrons + orbital contribution). Thus with the increase
of temperature, the observed magnetic moment increases. The observed magnetic susceptibility is
given by: .
ry
1 XO+5XM (5 T2g )exp(-M/kBT) .
ra
X
M
= 1+5exp(-M:/kB T) ,
M:=E
h.s.
-E
l.s.
ib
[Fe(NCS)2(phen)2l
yl
~
m
5
'" he
4 [F.e(NCSe)2(phen)2l
~
lc
ea
~ 3
:t
~
th
2
e/
r
t.m
0
100 200 300 400
e
~ T(K)
er
Fig. 8.24.5.2 Temperature dependence of lJ.eff for [Fe(phen)2X2] (X =NSC, NCSe). This is a case of abrupt
H
spin transition.
Note 1: The spin-orbit coupling integral for the interaction between the states 5T2g (h.s.) and 1A 1g
k
(l.s.) (i.e. L = 0) is zero.

lic
For the given Fe(II)-complexes, the spin transition curve indicates an abrupt change. This is also
refected in the plot, ~eff vs. temperature (cf Fig. 8.24.5.2).
C
Note 2: For the strong field ligands (i.e. higher ~o value), 1A 1g is the ground state while for the weak
field ligands (i.e. lower ~o values) 5T2g is the ground state.
(Note 3: Even at 0 K, there is a residual paramagnetism (which is called the temperature independent
paramagnetism i.e. TIP arising for the 1A 1g state interacting with the excited IT1g state capable of
making an orbital contribution (see 2nd order Zeeman effect, Sec. 8.22.2).
In fact, for [Fe(phen)2X2] (X = NCS, NCSe), at room temperature, both the high spin and 10'\' spin_
states exist in equilibrim and Jleff is determined by their Boltzmann population densiti.es. At a very l~· .
temperature, Jletf suddenly drops to a very small value (which is basically the TIP value originated from
the lA 19 ground state interacting with the 1T 1g excited state).
(ii) Fe(lll) complexes:

(A) The tris-dialkyldithiocarbamatoiron(lll) i.e. [Fe(dtc)3] or [Fe(S2CNR2)3] complexes experi-
ence the spin state isomerism controlled by temperature.
ry
Fe (III) i.e. [Fe(dtchl
ra
ib
The nephelauxetic effect (FellI ~ S i.e. the electron cloud is pushed into the vacant d-orbital of
yl
S through the n-bonding) reduces the pairing energy (P). It leads to the condition of spin state isomerism
m
i.e. P ~ 10Dq. This aspect has been discussed in Sec. 8.24.1. The temperature dependent equilibrium is:
e;, 6A
he
l.s. (~g, 2T2g ) ~ h.s. (fig 19)
The [Fe(dtc)3] ·complexes record an increasing trend of magnetic moment with the increase of
lc
temperature. At a very low temperature, the magnetic moment is 2.1 B.M. (ef Jlspin = 1.73 B.M.) which
ea
is due to mainly the low spin isomer. It may be noted that the low spin isomer possesses some orbital
contribution. With the increase of temperature, the observed magnetic moment gradually increases due
to the higher population density at the high spin state (possessing 5 unpaired electrons, Jlspin ~ 5.9
th
B.M.). Here, it may be pointed out that for [Fe(dtc)3]' even at a high temperature, the expected Jlspin
value of the high spin state is not attained, i.e. incomplete spin transition curve (ef Fig. 8.24.4.1). It
e/
is due to the fact that in terms of Boltzmann distribution law, all the molecules cannot be ther-
mally excited to the higher energy level.
t.m
At very low temperature, [Fe(dtc)3] shows the magnetic moment 2.1 - 2.3 B.M. which may be
considered as the magnetic moment of the low-spin isomer. For the corresponding high-spin isomer, the
expected magnetic moment is 5.92 B.M. (= Jlspin). In fact, the 6A lg term cannot introduce any orbital
e
contribution either from the ground state or the excited state. Thus we can write:
er
2 T2g (l.s.) ~ 6A Ig (h.s.), K eq ==~, a = mole fraction of the high spin state.
H
I-a
(J.1obs)2 = a(J.1h.s)2 + (1 - a)(J..I1.s)2 =a x (5.92)2 + (I - a) x (2.2)2

k
= 2.2 B.M., Jlh.s. = 5.92 B.M.,

lic
At room temperature, [Fe(dtc)3] records Jlobs ~ 4.3 B.M. Taking, Jll.s.

we can write:
C
(4.3)2 = a(5.92)2 + (1 - a)(2.2)2

It leads to a = 0.45 i.e. the equilibrium mixture consists of 45% of the high-spin isomer (6A Ig ) and
55% of the low spin isomer (2T2g ).
Here it is interesting to mention that the tris( dithiocarbamato)iron(III) complex i. e. [Fe(S2CNH2)3]
using the unsubstituted dithiocarbamate ligand predominantly exists as the high spin complexes
supported by the magnetic data (i.e. Jlobs = 5.80 B.M.). When the hydrogen atoms are substituted by the
alkyl groups, the complex shows the thermal equilibrium between the spin states.
The situation can be explained in terms of steric factors mainly determined by the size of R.
ry
(Steric interactions are indicated by the arrows)
ra
With the increase of bulkiness of R, a increases and it leads to decrease the angles ~ and 8. It is
ib
evident that increase in the steric repulsion between the R-groups leads to a small ligand bite. Thus the
bulkiness of R-groups can sterically control the ligand bite size of the FeS6 core. The contraction of
yl
bite angle (8) gives the shorter Fe-S bond length (i.e. higher 10Dq value) to favour the low spin
m
complex.
The critical temperature (Tc ) indicates the temperature at which the mole fractions of the high spin
he
and low spin states are both equal to 0.5. The Tc for the equilibrium,
low spin ( S = ~ ) ~ high spin ( S =%)

lc
ea
has been found to increase with the size of R i.e. with the increase of bulkiness of R, the low spin
complex is favoured more. Thus, Tc for R = isopropyl group is higher than that for R = methyl group.
It has been noted that for R =Me group, Tc shifts to about 200 K and for R =H, the steric interaction
th
is so minimised that the high spin state is attained in the whole temperaure range. Similarly, for the
e/
ligand, tetramethylene dithiocarbamate, the steric crowding is minimised and the corresponding Fe(lll)
complex prevails in the high spin state in the whole temperature range.
t.m
( ~
V /~'\
N -c~s ~Fe(III); (t~ge~. i.e. high spin)
e
er
For [Fe(dtc)3]' the general conclusion is:

H
• higher the steric crowding (i.e. bulkier R), lower the ligand bite size (i.e. smaller the bite angle 8) ~
shorter the FeIII-S distance (i.e. less the electron density in the eg-level and higher the lODq
k
value) favouring the low spin isomer.

lic
• lesser the steric crowding, higher"the bite angle (8) ~ longer the FeIII-S distance (i.e. more the
electron density in the eg-level and lower the lODq value) favouring the high spin isomer. .
C
Many Schiff base complexes of Fe(III) also display the spin state isomerism.
Note: The complex [Fe(dtc)3] i.e. [Fe(S2CNR2)3] shows the high spin -low spin equilibria but the
halido complex, i.e. halidobis(dialkyldithiocarbamato)iron(III), [Fe(dtc)2X] (X = CI, Br, I) obtained
from [Fe(dtc)3] by the action of HX shows the magnetic moment, J..lobs :::: 3.9 - 4.0 B.M. This observed
magnetic moment is in conformity with the three unpaired electrons. [Fe(dtc)2X] maintains the square
pyramidal geometry (C4v ) where Fe-centre lies about 65 pm away from the basal plane (i.e. less
repulsion experienced by the metal dxy orbital). The electronic configuration in terms of its structure
shown in Fig. 8.24.5.3 is:
(dxy)2 (dxz ) 1 (dyz)l (di)l (i.e. 3 unpaired electrons)
CI
d x2_ y2
I
4 dt
:';N-CCV/~!>-N(R 14 d XZl dyz
ry
4b d xy
S S R
ra
(b)
(a)
ib
Fig. 8.24.5.3 (a) Square pyramidal structure of chloridobis(N,N-dialkyldithiocarbamatio)iron(III). (b) Energy order of
the d-orbitals in a square pyramidal geometry (cf Fig. 8.15.1 for energy order of the d-orbitals).
yl
Here it is worth mentioning, that the said five coordinate complex of Fe(lll) is the classic example of
m
spin intermediate and this aspect will be discussed in Sec. 8.25.4.
(B) The Fe(III) complexes ofmonothio-p-diketonates i.e. [Fe{RC(S)-CH = C(O)R}3] experience
he
the thermally controlled spin state isomerism between the low-spin (~g) and high spin (~gei) states.
R",
c---s
lc
ea
//-----
'" --
HC , Felli
th
-O
C --- - -
R/
e/
An electron withdrawing R-group favours the metal to ligand back donation. It will reduce better the
t.m
Racah parameter (B) and consequently, the pairing energy will be reduced. This reduction in pairing
energy will favour the low-spin state.
(C) Thermal equilibrium between the high spin and low spin states of ferrihemeproteins is also well
e
established. From the magnetic data, the following distribution has been predicted.
er
% (h.s.) % (l.s.)
FeIlI-Hb (i.e. met-Hb) 50 50
H
FeIIl-Mb (i.e. met-Mb) 70 30

FellI_peroxidase
k
78 12
= hemoglobin, Mb = myoglobin).
lic
(Hb
The above distribution of ferrihemeproteins has been calculated by taking Jlh.s. = 5.92 B.M. and
C
ilLs. = 2.25 B.M. and using the relationship: (Jlobs)2 = u h.s.(Jlh.s)2 + (1 - u h.s)(JlLs)2.
(iii) Spin state isomerism in Co(II) (tP) complexes: The complex, bis(2, 6-pyridinedialdehyde-
hydrazone)cobalt(ll) iodide shows the magnetic moment 1.9 B.M. at 80 K while this value increases to
3.7 B.M. at 337 K. It indicates that with the increase of temperature, the fraction of high spin state
increases. [Co(terpy)2]CI 2· 3.5 H 20 also shows the spin state isomerism.
Taking, Jlh.s. = 5.2 B.M. (for t2~ e;, both spin contribution and orbital contribution; see Sec. 8.18.2),
ilLs. = 1.9. B.M. (for t2~ e;, taking the spin contribution as the main contribution), the distribution
between the spin states at a particular temperature can be calculated from the observed magnetic moment.
(Jlobs)2 = uh.s.(5.2)2 + (1 - U h.s)( 1.9)2
(iv) Spin state isomerism in Co(III) complexes: [CoF6]3- and [CoF3(OH 2)3] are the examples of.
high-spin complexes of Co(III). For [Co(OH 2)6]3+, P ::::: 20,000 cm- I , 10Dq ::::: 20,000 cm- l and the
complex remains in a spin state isomerism. The relatively high water exchange rate constant in
[Co(OH 2)6]3+ is partly due to the spin state isomerism.
8.24.6 Spin State Equilibrium in the Mixed Ligand Tetragonal Complexes of Nickel(lI)
ry
In the tetragonal complexes, [NiA4B 2], the degree of tetragonal distortion depends on the difference
in the crystal field strengths of the axial ligands (B) and equatorial ligands (A). Let us consider the
ra
splitting pattern of the d-orbitals in [NiA4 B 2] complexes.
ib
yl
m
he
lc
ea
th
e/
t.m
e
~
er
8
Paramagnetic for d
(D 4h )
8
H
Diamagnetic for d
(a) (b) (c)
k
Fig.8.24.6.1 Splitting of the d-orbitals in (a) octahedral geometry, (b) weakly tetragonally distorted complex,
lic
(c) strongly tetragonally distorted complex.
• If A and B are of similar crystal field strength, ~i and ~~ will be very small (i.e. P » ~i ) ~;) and
C
the electronic configuration will be:
weak tetragonal distortion: (d xz , dyzt (dXy )2 (d/ f (dx'-i r'(high spin) (2 unpaired electrons,
3.0 B.M.)
J.!obs :::::
• If the crystal field strength of the ligands A and B differs suffieciently to make A~ = P (Fig.
8.24.6.1 b), then the spin state isomerism will occur.
• If B is a much weak field ligand compared to A, then the severe z-out distortion will occur (i.e.
~~ will be very large; ~~ = ~l + ~2) and ~l will be much higher than the pairing energy P cf. Fig.
8.24.6.1c). It will lead to spin pairing i.e.
strong tetragonal distortion: (dxz , dyzt (d )2 (dxy)2 , (low-spin); (No unpaired electron; f..lobs '" 0)
Z2
(a) [NiCI 2(detu)4]: Under the condition, L\~ ::::: P ::::: kBT, the thermally controlled spin state isomerism
may occur. Let us illustrate the situation for [NiCI 2(detu)4] i.e. dichloridotetrakis(N,N'-diethyl-
thiourea)nickel(II) which is diamagnetic (i.e. ).lobs::::: 0) below 194 K but its magnetic moment increases
with the increase of temperature. It suggests the following equilibrium.
ry
[NiCI 2(detu)4] (low spin) ~ [NiCI 2(detu)4] (high spin).
ra
(Et)HN
ib
detu=N, N'-diethylthiourea, i.e. )c=s
(Et)HN
yl
With the increase of temperature, the equilibrium is shifted towards right side.
m
(b) [Ni(TAAB)X2]·H20: The monohydrate complex, [Ni(TAAB)X 2] . H20 (X = CI, Br) also shows
he
the spin state isomerism in its tetragonal structure. TAAB is a planar quadridentate ligand and it is
tetrakisanhydroaminobenzaldehyde.
lc
ea
th
e/
t.m
x
(trans-axial ligand)
e
x
er
H
k
lic
C
Fig. 8.24.6.2 Structure of [Ni(TAAB)X 2] where TAAB = tetrakisanhydroaminobenzaldehyde and trans-axial

ligands are X-, X-.
[Ni(TAAB)]2+ is obtained in a template synthesis through the condensation of ortho-

aminobenzaldehyde in presence of a suitable Ni(II) salt in an alcoholic medium. If X- is a noncoordinating
bulky anion like CI04, BF4, PF6 etc, then the anhydrous complex is diamagnetic i.e. X- resides outside
the coordination sphere and [Ni(TAAB)]2+ adopts a square planar geometry. For the less bulky
coordinating anions like X- = SCN-, 1-, NO)", etc., the complex is tetragonal and magnetic moment
is close to 3.2 B.M.
(c) [Ni(TAAB)]X2 : Square planar; singlet, diamagnetic, bulky and non coordinating X- resides
outside the coordination sphere, (X- = CIOi, BFi, PF6", etc.)
(d) [Ni(TAAB)X 2]: Tetragonal, triplet, paramagnetic (}lobs - 3.2 B.M.), relatively less bulky and
coordinating X- resides within the coordination sphere (X- = SCN-, 1-, NO)).
(e) [Ni(TAAB)X2]·H20: For, X = CI, Br, it forms a stable monohydrate complex and the magnetic
ry
moment of the monohydrate complex is temperature dependent. At room temperature, the observed
magnetic moment is -1.6 B.M. (cf. Jlobs ::::: 0 for singlet, Jlobs ::::: 3.2 B.M. for triplet). The nature of
ra
temperature dependence of the magnetic moment indicates the following spin state isomerism for
[Ni(TAAB)X 2] • H 20 (X = CI, Br).
ib
tetragonal-singlet tetragonal-triplet
yl
2 2 2
(d x;:, d y;:) 4 ( d;:2 ) ( d xy ) (dx;:, d y;: ) 4 ( d xy ) ( d;:2 ) I ( d x2 _ y2 ) I
m
In the tetragonal-singlet state, the d Z2 orbital is filled in and consequently the approaching axial
ligands along the ±z directions face a more repulsion and it makes the 'Ni-X' bond relatively weaker
he
(i.e. Ni-X bond is longer). On the other hand, in the tetragonal-triplet state, the d Z2 orbital is half-
lc
filled and the approaching axial ligands along the ±z directions experience relatively a less repulsion.
It makes the Ni-X bond relatively stronger. It indicates that in the singlet state (where X- is weakly
ea
bound to the metal centre), the residual or unneutralized negative charge on X- is more compared to the
case of triplet state where X- is more strongly bound to the metal centre. This residual charge on X-
th
allows the H-bonding interaction with the H20 molecule residing outside the coordination sphere.
Obviously, this H-bonding interaction is more favoured in the singlet state over the triplet state
e/
because in the singlet state, the residual charge on X- is more.

• An unusual ligand field strength order of the halides in [Ni(TAAB)X 2 ]· H 2 0: The said
t.m
H-bonding interaction in [Ni(TAAB)X 2]· H 20 (X = CI, Br) is supported by the fact that the attempt to
prepare the anhydrous salt through vacuum drying leads to the elimination of HX not H 20.
In the said complex, for the halides (CI-, Br-, 1-), the iodide appears as the strongest field ligand.
e
This is an anomalous order. It can be rationalised by considering the fact that among the halides, 1-
er
(having the smallest charge density) is the least efficient one to introduce the H-bonding interaction
with the H 20 molecule residing outside the coordination sphere. Thus for X- = 1-, the triplet state
H
(where X- is more tightly bound with the metal centre) is the predominant form while for X- = CI-,
Br-, the singlet state is the most predominant one (where X- is relatively weakly bound with the metal
k
centre but more strongly interacting through the H-bonding with the H 20 molecule). The triplet state
lic
leads to minimise the z-out distortion to favour the octahedral geometry. Thus, in the triplet state, the
axial ligands appear as the stronger field ligands.
C
For the weakly bound axial ligands, the z-out distortion is high to favour the singlet state. Thus in the
triplet state, the axial ligands appear as the good coordinating ligands indicated by the reduced metal-
axial ligand bond length. In other words, in the triplet state, the axial ligands appear as the relatively
stronger field ligands compared to the case of singlet state where the metal-axial ligand bond is relatively
longer. It makes 1- a stronger field iigand than CI- and Br-.
8.24.7 Spin State Isomerism in the Square Planar Complexes (cf. Sec. 8.15c)
The tetragonal elongation of an octahedral geometry produces the square planar geometry in a linliting
situation.
ry
ra
ib
yl
m
he
lc
ea
th
Fig. 8.24.7.1 Splitting of d-orbitals in (a) octahedral (b) weak tetragonal distortion and (c) strong tetragonal
distortion leading to a square planar geometry.
e/
(Note: In a weak tetragonal distortion, the d ~2 orbital may lie above the dxy orbital. In the limiting
t.m
situation, the d ~2 orbital may lie energetically below the dxz. and d vz orbitals.)
For the cP, d7 and J6 configurations, the spin free and spin paired complexes are theoretically
possible (ef Table 8.24.7.1).
e
Table 8.24.7..1 Spin-free and spin-paired square planar complexes

er
Spin-paired Spin-free
H
ei al~ or al~ e1 e,~ al~ b2,~ bl~ or al~ e; b2~ bl~

(1 unpaired electron) (5 unpaired electrons)
k
Condition: ~b ~2 ) P Condition: ~l' ~2' ~3 ( P

e; e;
lic
al~ b2~ or al,~ b2~

(3 unpaired electrons i.e. intermediate spin)
C
Condition: ~ 1 ) P; ~2' ~3 ( P
d': e: alZ b2~ or al; ei b2~ ei al~ b2~ bl~ (weak tetragonal distortion)
(I unpaired electron) or al; ei b2~ bl~
Condition: ~l ) P (3 unpaired electrons)
Condition: ~l' ~2 ( P
cf': e: al; b2.~ ei al; b2~ bl~ (weak tetragonal distortion)
or al; e.: b 2; or al; ei b2~ bl~
(No unpaired electron) (2 unpaired electrons)
Condition: ~l ) P Condition: P ) ~l
Here it is important to mention that no high spin square planar complex or low spin ~ high spin
isomerism is reported for Ni(II) (d 8 ) and Co(II) (d7 ) square planar complexes. However, for
the Mn(II)-phthalocyanine complexes (cP system), the observed magnetic moment (i.e. ~obs::::: 4.5 B.M.)
indicates the partial spin pairing. The complex may exist in a spin state equilibrium where the
intermediate high spin state (i.e. al~ ei b2~) with three unpaired electrons (i.e. Ils = 3.87) is the
predominant one because, ~obs (= 4.5 B.M.) lies close to the expected magnetic moment of the inter-
ry
mediate high spin state with 3 unpaired electrons. The said high spin state does not have any orbital
contribution from the half filled eg level (ei), but the excited state (i.e. al~ e~ b2~) can introduce an
ra
orbital contribution through the spin-orbit coupling.
ib
8.24.8 Spin State Isomerism in the Five Coordinate Complexes (cf. Sec. 8.15c)
yl
Depending on the situation, in both the trigonal bipyramidal (D 3h ) and square pyramidal (C4v ) geometries,
the high spin and low spin complexes may exist. There may be an equilibrium between the two spin
m
states depending on the condition. The energy orders of the d-orditals in the given geometries are given
he
below.
D 3h (TBP): d X2 _ y2 > dXz.' d vz
d Z2 »dxy, }.
. . (see FIg. 3.5.8.2)
C 4v (Square pyramid): d X2 _ y2 > d Z2 > d xy > d xz ' d yZ lc
ea
For the square pyramidal geometry, the energy order, dx:' dyz ) dxy prevails when the metal centre-lies
above the basal plane (cf Fig. 8.24.5.3) and good n-bonding occurs at the basal plane.
th
8.25 MAGNETIC PROPERTIES OFTHE INTERMEDIATE SPIN AND SPIN ADMIXED

STATES IN THE FIVE COORDINATE SQUARE PYRAMIDAL AND SQUARE
e/
PLANAR COMPLEXES (cf. Sec. 8.15)

t.m
8.25.1 Possible Spin States and Intermediate Spin State

The splitting pattern of d-orbitals in a square pyramidal geometry (C4v ) can be obtained by removing
one axial ligand (i.e. z-out distortion) from an octahedral geometry.
e
The relative energies of the e (i.e. dxz ' dyz ) and b2 (i.e. dxy ) orbitals originated from the octahedral t2g
set depend on the extent of in-plane and out-or-plane 'It bonding interaction between the metal and
er
ligands in the basal plane (i.e. xy-plane).

H
/////
~~//------~------
," d X2_ y2 (b 1 )
~1
k
/// ===e=g==~'-,~::,-,~: --------------

lic
C
/ ' .. ~ d/ (a 1)
I
I
I
I ~2
~~~~ ~,~:~,-,~:~,~ --------- -~-~::~~ -~:

-- ' d,y (b
2
)
~=====~~:---------,;-------
t 2g dXZl dyz (e)
Fig.8.25.1.1 Splitting pattern of the d-orbitals in a square pyramidal geometry ofC 4v symmetry (cf Figs. 3.5.7.1,8.15.1).
• If the ligands like porphyrin or phthalocyanin having the conjugated n-bonds coordinate at the
basal plane then the b 2 (i.e. dxy ) orbital may be slightly more stabilised than the e (i.e. d xz and dyz ) set.
In such cases, the energy order becomes:
b I (d x 2 _),2 ) > a l (d Z2 ) > e (d xz' d yz ) > b2 (d xy ).

In absence of 7t-bonding in the basal plane, the order is:
ry
b l (d x2 _.i ) > a l (d Z2 ) > b2 (d xy ) > e(dxz ' d yz )· (cf Fig. 3.5.7.1; Chapter 3)
ra
• If the metal lies above the basal plane (i.e. xy-plane) then the metal dx.v orbital becomes relatively
more stabilised (cf the dxy orbital experiences the le~s repulsion from the basal ligands) and the
ib
above energy order (cf Fig. 8.24.5.3) of the orbitals is maintained.
yl
Thus for the sake of simplicity, it can be reasonably argued that the energy difference (~3) between
the e (i.e. dxz ' d yz ) and b 2 (dX),) subsets of the orbitals originated from the octahedral t2g orbitals is very
m
small. Thus we can write:
he
b l ( d x 2_ y2 ) > a I ( d Z2 ) > b2 ( d xy ) - e (d xz' d yz) (i. e. ~ 3 ~ 0) .
Now let us consider the distribution pattern of electrons of tF (e.g. FellI) and cf (e.g. Fell) systems:
A. d S: (i) (d xz ,dyz )2 (dxy)1 (d Z2 f (d x2 _l r when ~I'

lc
~2 P

e/
( Low Spin, 2 E i.e., S = ~ )

t.m
(iii) (dxz ' dy} (dxy)' (d Z2 )' (d x2 _l t when ~\ > P but ~2 < P
%)-
e
(Intermediate spin state, 4 A2 i.e. S =

er
Thus in the case of tF configuration, theoretically three spin states, i.e. 6A., 4A 2 and 2£ may arise in
H
a C4v symmetry. The low spin state (i.e. 2E) arises only when ~., ~2 ) P, but such a situation has not yet
been characterised in reality. Thus, the 4 A2 ( S = %) may be considered as the intermediate spin state:
k
r
lic
B. tf': (i) ( dxz' dyz )3 (dxy f (dZ2 f (dx2-l when ~\' ~2 P but ~2 < P (Intermediate spin, S = 1)
Thus we can conclude as follows:
(i) for the d 5 configuration, in a square pyramidal geometry, S = ~ and S = ~ are the two limiting
2 2
1.
situations while S = is the intermediate spin state.
2
(ii) for the tJ6 configuration, in a square pyramidal geometry, S = 2 and S = 0 are the two limiting
=
situations while S 1 is the intermediate spin state.
8.25.2 Possible Spin States and Intermediate Spin State in the Four Coordinate
Square Planar Complexes (cf. Sec. 8.15)
The orbital splitting pattern is shown in Fig. 8.24.7.1. The energy order of the orbitals is:
ry
eg (d xz ' dyz ) < a lg (d Z2 ) < b2g (dxy) < big (d x2 _ y2 )
ra
However, in some cases (where z-out tetragonal distortion is very high), al g may be of lower energy
ib
than ego Then the energy order becomes as follows:
(d Z2 ) < eg (d xz ' dyz ) < b2g (dxy) < big (dx2 _ y2 )
yl
a lg
m
Thus we may conclude that the energy difference (~3) between the a Ig and eg set is very small i. e.
~I (energy difference between big and b 2g ) ) ~2 (energy difference between b 2g and al g or eg) » ~3
he
(energy difference between al g and eg ).
Considering the energy order of the orbitals as follows:
a lg < eg < b2g < big

lc
ea
~~~
th
we can have the following situations (ef Table 8.24.7.1):

~
Low spin High spin Intermediate spin

e/
23bobO
alg eg 2g Ig alg eg2blbl
I
2g 19 al~ e; b1
g bl~
t.m
(~h ~2 ) P) (~b ~2' ~3- ( P) (~l ) P

but ~2 ( P)
1 unpaired electron, 5 unpaired electrons, 3 unpaired electrons
S=~·(6A ) S=~·(4A )
e
2' I 2' 2
er
ali ei b2~ bl~• ali e; b2~ bl~ ali ei b1g bl~

(~b ~2.) P) (~b ~2' ~3 ( P) (~l ) P but ~2 ( P)
H
diamagnetic, 4 unpaired electrons 2 unpaired electrons

(S = 0) (S = 2) (S = 1) .
k
lic
Mn(II)-phthalocyanine complex shows Ilobs = 4.5 which is too high for S =! and too low for
2
C
S = ~ . The observed magnetic moment corresponds to the intermediate spin state, S = ~ (i.e. Ils pin =
2 2
3.87 B. M.). The observations, Ilobs) Ils can be explained by considering the orbital contribution from
the excited state, i.e. ali e; b2i bl~ through the spin-orbit coupling. Here it is worth mentioning that the
i
ground state (ali e; b 2 bl~) having the half-filled eg level (dxz ' dyz ) cannot make any orbital contribution.
[FeII(TPP)] (TPP =meso-tetraphenylporphyrinate) is a square planar complex with the intermediate
spin state S = 1 (ali ei i
b 2 bl~). It may be noted that the ei
level can make some orbital contribution
at the ground state.
1194 FUNDAMENTAL CONCEPTS OF JNORGANIC CHEMISTRY
8.25.3 Quantum Mechanical Spin-Admixed Ground State

For the tP-system, in a square pyramidal geometry (C4v ), three possible ground states are:
6 Al ( 5=25) ' 4 A 2 ( 5=23) and 2 E ( 5=21) ; (cf Sec. 8.25.1) .
ry
The low-spin state characterised by 2E is not really attained in any complex. Thus we may consider
(s %) and intermediate spin state (s = %) are the common ground states
ra
that the high spin state =
ib
depending on the ligand field strength.
Depending on the ligand field strength, the 6A I and 4A 2 states may be comparable in energy and then
yl
they can mix quantum mechanically to generate the quantum mechanical spin-admixed ground
m
state. The degree of mixing between the states depends on the energy separation and spin orbit coupling
constant. Similarly, for the d 6 system~ in a square pyramidal geometry (cf Sec. 8.25.1)~ the spin-
he
admixed state may arise.
8.25.4 Magnetic Properties of the Square Pyramidal Complexes of Fe(lIl) in Terms of

lc
Intermediate Spin and Spin-Admixed States
ea
The halidobis( dialkyldithiocarbamato)iron(III) i. e. [Fe(dtc )2X] is the classic example of the interme-
%). In the distorted structure, the axial position is occupied by halide and Fe(III)
th
diate spin state ( S =

lies about 60 pm above the basal plane (cf Fig. 8.24.5.3). At room temperature, the observed magnetic
e/
moment (3.9 - 4.0 B.M.) corresponds to three unpaired electrons (i.e. intennediate spin state 5 = 3/2).
t.m
Fe(III)-porphyrin systems can show the situations of low spin, high spin, spin intennediate and
spin-admixed state-depending on the axial ligand field strength.
Five coordinate [FeCI(TPP)] (TPP = meso-tetraphenylporphyrinate) shows the spin state 5 = 5/2
(i.e. high spin) and in this complex, Fe(III) lies about 50 pm above the porphyrinato plane. The
e
Fe(III)-N bond length 207 pm is probably larger than the cavity radius at the basal plane.
er
If chloride is replaced by a moderately strong field ligand then it leads to S = ~ ground state (i.e.
H
- 2
intermediate spin state) or spin-admixed ground state arising from 5 =~ (high spin) and 5 =~
k
2 2
lic
(intermediate spin). In [Fe(CI04 )(TPP)], CI0 4 ligates along the axial direction by using one of its four
C
O-sites. Here, the Fe(III)-N bond (= 200 pm) is relatively shorter than the Fe(III)-N bond (= 207 pm)
of [FeCl(TPP)] which remains in high-spin state (s = %). In fact, in [Fe(Cl04)(TPP)] the spin-ad-
mixed state is attained and the radius of Fe(III)-site decreases compared to the situation of high-spin
state (cf the metal-ligand bond length increases with the increase of high-spin character). In the
spin-admixed complex, Fe(III) centre lies about 28 pm above the basal plane. At room temperature, XMT
of [Fe(CI04 )(TPP)] is about 3.2 cm 3 mol- l K which is significantly higher than 1.9 cm 3 mol- l K
(anticipated for the pure intennediate spin state S = ~) and also significantly lower than 4.4 cm 3
2
mol- l K (anticipated value for the high spin state 5 = ~). This magnetic data support the spin-
2
admixed ground state in [Fe(CI04 )(TPP)].
Note: For the strong axial ligands, [Fe(TPP)]+ leads to the low spin 6-coordinate complex, e.g.
[Fe(CN)z(TPP)]- (tz~ e~, i.e. 5 = 1/2). With the neutral and weak field axial ligands, high spin
ry
6-coordinate complexes, e.g. [Fe(OHz)z(TPP)]+ (tzi ei, i.e. 5 = 5/2) are produced.
ra
8.25.5 Magnetic Properties of the square Pyramidal Complexes of Fe(lI) in Terms of
the Intermediate and Spin-Admixed States
ib
[FeIIL(TPP)] may have the different spin states (cf. Sec. 8.25.1) depending on the ligand field strength
yl
of the axial ligand (L).
= strong field ligand like NO, CO, etc., low spin complex (5 = 0).
m
L
L = weak field ligand like 2-methylimidazole, high spin complex (5 = 2).
he
The planar complex, [Fe(TPP)] shows the intermediate spin state 5 = 1.
lc
8.25.6 Thermally Controlled Spin Equilibrium Involving an Intermediate Spin
ea
Sometimes, the intermediate spin state may remain in an equilibrium with the high-spin or low spin
state. The most well studied example in this class is: [Fe(NO)(salen)]+ where salen = N, N'-ethylep.ebis-
(salicylideneiminate). It adopts the square pyramidal geometry. There is an spin equilibrium between
th
the states S =.!.. (low spin) and S =l (intermediate spin) arising from the tF system of Fe(III) (cf. Sec.
e/
2 2
8.25.1 for the possible spin states). With the increase of temperature, there is an abrupt spin transition
t.m
at about 175 K from the 5 =! to S =~ spin state. In the square pyramidal geometry of [Fe(NO)(salen)]+,
2 2
Fe(III) coordinates with the tetradentate ligand salen (NzO z) in the basal plane while bent NO binds
° angle is about 140
e
/\
0
along the axial direction. Above the transition temperature (-175 K), Fe - N-
er
while below the transition temperature, the angle is about 125 0 •

H
Experimental verification of the existence of spin state equilibrium

k
The anomalous magnetic moment may arise in two ways: there may be a mixture of fixed
lic
composition of two different spin states which do not remain in equilibrium; there may be a spin-
state equilibrium. In the first case, composition of the mixture will not change with the change of
C
temperature but in the second case, composition of the mixture will change with the change of
temperature. In such cases, the Curie-Weiss plot will be nonlinear. If it is a mixture of fixed
composition of two different states (say 5 = 1 and 5 = 0), then the linear Curie-Weiss plot for the
S = 1 state will be maintained. Thus, from the nature of Curie-Weiss plot, the cases may be
distinguished.
Spin state equilibrium between the spin states S = 1/2 and S = 3/2 has been found to prevail in the
Fe(III) complex, [Fe(NO)(TMC)](BF4)3 where TMC stands for 1, 4, 8, II-tetramethyl-l, 4, 8, 11-
tetraazacyclo-tetradecane.
Me", (l/Me
N
CN NN) (TMC)
Me/V "Me
ry
ra
8.26 STRUCTURAL ISOMERISM LEADING TOTHE SPIN STATE EQUILIBRIUM
ib
Sometimes, a complex may adopt different stereochemical configurations provided their energies differ
only marginally. The energy difference is of the order of thermal energy kBT. Under this condition, the
yl
complex may produce an equilibrium mixture of different geometrical configurations and a slight
change of the conditions may shift the equilibrium towards a particular stereochemical configuration.
m
If the different structures possess different numbers of unpaired electrons then it may lead to an
he
equilibrium between the two different spin-states.
Different types of structural equilibria leading to an anomalous magnetic moment will be discussed
here.
lc
ea
8.26.1 Octahedral - Square Planar Equilibria for the Nickel(lI) Complexes
(cf. Sees. 8.24.6, 7.17.2)
th
Many singlet square planar (i.e. diamagnetic) complexes of Ni(II) can add two unidentate ligands
(which may be the solvent also) in the axial directions giving rise to the octahedral (more correctly
e/
tetragonal) structures.
J
[Ni L 4 + 2L' ~ trans-[NiL 4 L;]
t.m
II
(singlet) (triplet)
Sometimes, the square planar and square pyramidal complexes of Ni(II) may remain in an equilibrium.
e
[NiL4 ] + L' ~ [NiL4L']

er
(a) [NiL]2+ when L = macrocyclic tetradentate ligand (N 2S2) can form different types of complexes
depending on the nature of anion.
H
with perchlorate: [NiL](CI04 )b diamagnetic, square planar, red

with halides: [NiLX]X, (X = CI, Br, I), square pyramid, paramagnetic
k
with 2 unpaired electrons, blue - green.

lic
with NCS-: [NiL(NCS)2], octahedral (i.e. tetragonal) paramagnetic

with 2 unpaired electrons, violet.
C
A similar situation for the macrocyclic ligand TAAB (N4 ) has been discussed earlier (see Fig.
8.24.6.2),
(b) The Lifschitz salts (named after the discoverer) are the classic examples showing the square
planar ~ octahedral equilibrium. The substituted ethylenediamine can produce the blue (paramagnetic)
and yellow (diamagnetic) complexes with Ni(II) depending on the conditions like the nature of anion,
solvent and temperature.
ry
' "C - - NH2 2
H - - C/
N '"
C--N
H 2 L H
N--C
2 / l2+
"'Ni~ (I )Ni~ I)
ra
'"
1
/ I I'"
'" + 2L
I
ib
C--N
/ N--C
/ C--N N--C
/ H2 H2 '" / H2 L H2 '"
yl
(Square planar), diamagnetic, yellow (Distorted Octahedral or tetragonal)
m
paramagnetic blue, (J.l ~ 2.9 8.M.)
he
Lifschitz salts have been characterised in solid state with various types of anions like CI-, Br-, 1-,
CI04-, RC0 2-, etc. Some of these salts are yellow and some of these are blue. Some salts change from
yellow to blue on heating and back again to yellow upon cooling. lc
Heating,
ea
Yellow salt , Blue salt.
Cooling
Sometimes, the yellow salt becomes blue when dissolved in the coordinating solvents. Thus
th
recrystallisation of yellow salts from· the coordinating solvents leads to the blue salts which may be
again converted into the yellow salts through the removal of solvent (e.g. dehydration in the case of
e/
water as the solvent).

t.m
blue colouration recrystallisation

Yellow salt coordinating) ) Blue salt.
solvent (in solution)
l
e
R_e_m_o_v_a_1o_f_s_o_lv_e_nt _____
er
In the unit cell of Lifschitz compound, solvated bis(meso-stilbenediamine )nickel(ll) dichloroacetate,

H
there is one square planar centre and two distorted octahedral centres attained by the coordination of
anion or solvent. Thus the observed magnetic moment is:
k
2 1 2 2 2
="3 J.l(square planar) +"3 J.l(octahedral)
lic
J.lobs
2
C
2 .
::= 3" J.l(octahedral) ; (taking J..l(square planar) ::= 0)
J.lobs=2.6 B.M. It leads to: J.l(octahedral) ::= 3.2 B.M. which is in good agreement with the expectation.
Note: The variable properties (colour and magnetic moment) of Lifschitz salts depending on the nature
of anion, solvent, exposure to atmospheric moisture, etc. bewildered the chemists for several decades.
Now these are rationalised in terms of the octahedral-square planar equilibrium.
(c) [cis-Ni(OH 2)2(trien)]2+: In solution, it changes the blue colour to yellow colour with the addition
of inert salts. The colour change, blue to yellow supports the structural change, octahedral to square
planar. Thus it supports the following equilibrium.
1198 . FUNDAMENTAL CONCEPTS OF INORGANIC CHEMISTRY
Ni
//Ni~/
I I
'/I~'
ry
+
C-r------
, I '
I I '
I I I
OH2 N----------------N
ra
~
ib
[Ni(trien)]2+
Cis-[Ni(OH 2)2(trien)] 2+ (square planar, yellow, diamagnetic)
yl
(octahedral, blue, paramagnetic)
m
The square planar form predominates at the higher temperature. Similar equilibria have been argued
for [Ni(en)2(OH 2)2]2+ and [Ni(OH 2)2(pn)2]2+
he
(d) Bis(salicylaldoximato)nickel(II) is diamagnetic and colourless but when dissolved in pyridine,
the solution becomes green and from the solution, green coloured paramagnetic crystals may be isolated.
lc
ea
th
e/
t.m
(Colourless, diamagnetic)
©
e
er
(Green, paramagnetic)
The given complex shows the diamagnetic behaviour in the noncoordinating solvents like benzene.
H
(e) Depending on the condition, the [Ni II L 2] complex [where LH = the Schiff base ligand obtained
from condensation of salicylaldehyde with the substituted ethylenediame (1: 1)] can remain in an equi-
k
librium, between the octahedral (tridentate 0, N, N character of the ligand) and square planar (bidentate
lic
0, N character of the ligand) geometries.

C
[Ni(Lh] [Ni(L)2]
(Diamagnetic, (Paramagnetic
Square planar) Octahedral)
Bidentate (0, N) Tridentate (0, N, N)
function of L function of L
(LH)
Position of the equilibrium depends on the nature of the substituents R 1 and R 2 and temperature.
(0 The salt, [Ni(CI0 4)2(PY)4] can also remain in the following equilibrium.
(Square planar, yellow, diamagnetic) [Ni(pY)4](CI04)2 ~ trans-[Ni(CI04)2(pY)4] (Tetragonal, blue,
paramagnetic)
Note: Generally, CI04 does not act as a good ligand.
ry
8.26.2 Monomer-Polymer Equilibria among the Nickel(lI) and Cobalt(lI) Complexes
Sometimes, through polymerisation, an octahedral arrangement is attained. Depolymerisation in the.
ra
noncoordinating solv~nts produce the square planar monomer. It is illustrated for some Ni(II) complexes.
(a) [Ni(acac)2] is a square planar complex but readily it may undergo trimerisation in which the
ib
octahedral stereochemistry around Ni(II) is attained. The trimerisation is indicated by the increase of
yl
magnetic moment. The trimer of [Ni(acac)2] is very stable and the monomeric form is detected when
the trimer is dissolved in a non-coordinating solvent at high temperature (ca. 200°C). If the trimer.
m
is dissolved in a coordinating solvent like pyridine, the trimer breaks down and gives the solvent
coordinated monomer.
he
[Ni (acac)] 3~[ Ni (acac)2(pY)2 ]
lc
However, If the Me group of acac is substituted by the bulky CMe3 group then polymerisation is
ea
prevented due to the steric hindrance and the diamagnetic monomer predominates.
~
th
o 0
o
e/
f\
t.m
o 0
o
o 0
~
e
er
Fig.8.26.2.1 Schematic representation of the trimeric structure of [Ni(acachl, i.e. bis(acetylacetonato)nickel(II) show-
H
ing the octahedral coordination around Ni(II).
If the Me group of acac is substituted by the alkyl groups of intermediate size, e.g. isopropyl or the
k
H-atom of the central CH group is replaced by a phenyl ring, then the sterle crowding is not sufficiently
lic
large to prevent the polymerisation totally. Under the condition, the partial polymerisation of [Ni(L)2]
leads to an equilibrium between the square planar diamagnetic monomer and the octahedral
C
paramagnetic polymer. When such a complex is dissolved in a noncoordinating solvent, the spectral
and magnetic properties depend on the temperature and concentration.
in noncoordinating )
( solvent
.........
[Ni (L)2 3 J _6_S_~~..... 3[ Ni (L)2 (S)2 ]
octahedral stereochemistry) (octahedral)
( ofNi ll
(S = Coordinating solvent like H20, py)

[Ni(L)2l (predominantly square planar monomeric form).
(Polymerisation is prevented due to the steric crowding).
ry
ra
R
"C--O
- /, ._----
J
x[Ni (L)i ~ [Ni (L)2 J
ib
L = HC: - , x
"\.'----- (Square planar) (Octahedral)
C--O
yl
R/
m
(R = i-Pr)
he
x[ Ni (L)2 J~ [Ni (L)2 Jx
lc
(Higher concentration favours the polymerisation and
ea
it increases the magnetic moment)
.. (b) Bis(N-methylsalicylaldiminato)nickel(II) when dissolved in the noncoordinating solvents like

th
C6H6 or CHCl 3 produces an equilibrium mixture of the monomer (square planar) and the dimer with
e/
the 5-coordinate (square pyramidal stereochemistry) high-spin Ni(II).

t.m
e
er
H
k
lic
(a)
C
(b)
Fig. 8.26.2.2 Structure of bis(N-methylsalicylaldiminato)nickel(II). (a) Monomeric form (square planar). (b) Dimeric
form showing the square pyramidal structure of Ni(II)
2[Ni(L)2J LH = N-methylsalicylaldimine
(Square planar, monomer, Square pyramidal, high-spin Ni(II)
singlet, diamagnetic) centre, dimer, triplet, paramagnetic.
When the complex is dissolved in the coordinating solvents like py or water, it produces the solvent
coordinated octahedral monomer, i.e. [NiL2] + 2S ~ [NiL 2(S)2]
If the concentration of the complex in the noncoordinating solvents is increased, the chance of
dimerisation increases and the magnetic moment increases.
The extent of dimerisation can again be controlled sterically. In the dimerisation process, phenolic
oxygen acts as the bridging donor site. If a bulky group (R) is introduced at the ortho-position of the
phenolic OH group, then the steric crowding does not allow the phenolate oxygen to act as the bridging
donor site. Then the complex predominantly exists in the monomeric (dimagnetic) form. If the substi-
ry
tution is carried out at the para-position of the phenolic OH group, then substitution cannot hinder the
dimerisation process and the square planar ~ square pyramidal equilibrium is not disturbed.
ra
It may be noted that for Co(II), the monomer is a tetrahedral one (ef. NiH is relatively more reluctant
to have the tetrahedral structure) but in the dimer, the square pyramidal geometry is attained as in the
ib
case of Ni(II).
yl
(c) [Co(acac)2] can exist as a stable tetramer in which the high spin octahedral stereochemistry is
attained around the Co(ll) centre.
m
he
o
lc
ea
o 0
~
th
e/
H
H3C , ~C............ /CH 3
f \0 C ,"--", C
t.m
o I " - '. I
0' '0
(acac-)
e
Fig. 8.26.2.3 Schematic representation of the tetrameric structure of [Co(acach], i.e. bis(acetylacetonato)cobalt(II)
showing the octahedral coordination around Co(ll).
er
The monomer is tetrahedral. When the tetramer of [Co(acac)2] is dissolved in a noncoordinating

H
solvent, the monomer is found to remain in an equilibrium with the tetramer in which Co(ll) maintains
the distorted high spin octahedral geometry.
k
4[Co(acac)2J ~ [Co(acac)2J4' (at high concentration in the non-coordinating solvents)

lic
Here it may be mentioned that in both the tetrahedral and high-spin octahedral geometry, the number
i
of unpaired electrons is the same (ef t2 ei in 0h and e4 ti in Td ). The orbital contribution in the
C
ground state of high spin octahedral geometry is possible but it is not possible for the tetrahedral
geometry. However, the tetrahedral geometry can experience a positive orbital contribution from the
excited state (e 3t1) through the spin-orbit coupling but it is relatively less important compared to the
ground state orbital contribution. In fact, in general, for Co(II), Jlobs of the high-spin octahedral
geometry is higher than that of the tetrahedral geometry (see Sec. 8.18.2). Thus, the observed
magnetic moment depends on the position of the equilibrium.
Again the steric-steric crowding on the acac ligand can prevent the polymerisation. In fact, if the
Me group is replaced by CMe3 (i.e. tertiary butyl group) then the polymerisation is prevented and the
tetrahedral monomeric form predominates.
8.26.3 Square Planar-Tetrahedral Equilibrium of Ni(lI) Complexes

(cf. Secs. 2.3, 7.17.2, 8.26.1)
(a) [NiL 2X2] (L = substituted phosphine ligand, X = halide) can remain in the following' equilibrium.
L
ry
I
X/7"'-L . .
ra
11 '>
ib
(paramagnetic, triplet (diamagnetic, singlet
~ ::= 3.20 8.M., blue-green) ~ ::= 0, red-yellow)
yl
The effective magnetic moment is given by:
m
2 2 2 2
J.letT =a + aspJ.l sp ~ a Td J.lTd '
Td J.lTd
he
a Td = mole fraction of the tetrahedral configuration; asp = mole fraction of the square planar com-
plex; a Td + asp = 1.
J.lsp = magnetic moment of the square planar configuration taken to be zero.
lc
For the complex, [NiBr2(PEtPh2)2], in the noncoordinating solvent CH 2CI 2, Jleft is found 2.7 B.M.
ea
«J.lTd ~ 3.20). It indicates a Td ~ 0.7 and asp ~ 0.3, i.e. in solution the paramagnetic tetrahedral form
(green in colour) is about 70% while the diamagnetic square planar form (red in colour) is about 30%.
th
Sometimes, it may be possible to isolate them in pure forms from their equilibrium mixture.
For the tetrahedral ~ squar~ planar equilibrium of [NiL2X 2], the tetrahedral configuration is favoured
e/
in the order: X =I ) Br ) CI and L =Ar3P ) Ar2RP ) ArR 2P ) R 3P (where Ar =aryl group like phenyl and
'R = alkyl group). Obviously, the steric crowding favours the tetrahedral configuration where the
t.m
bond angle is larger. Crystal field stabilisation energy favours the square planar geometry but the
steric factor favours the tetrahedral geometry. These two opposing factors control the position of the
equilibrium.
e
In the unit cell of bis(benzyldiphenylphosphine)dibromidonickel(II), i.e. [~iBr2{P(CH2Ph)Ph2}2]'

two Ni(~I) centres maintain the tetrahedral geometry and one Ni(ll) centre maintains the square planar
er
geometry. Thus we can write:

H
2 1 2 2 2
J.lobs ="3 J.l(square planar) + "3 J.l(tetrahedraJ)
k
2 2 .
= "3 J.l(tetrahedral), (takIng J.l(square planar) ~ 0)
lic
The observed magnetic moment is 2.7 B.M. It leads to J.l(tetrahedral) = 3.3

B.M. which is in good
C
agreement with the expectation.

Intrallogons: The spin isomers which only differ in bond angles are described as intrallogons (allos
meaning different and gonia meaning angle). Thus, the square planar and tetrahedral spin isomers are
the examples of this group.
(b) Molar volume (VM) of a tetrahedral complex is relatively higher than that of its square planar
isomer. Thus', the equilibrium, tetrahedral ~ square planar, will be shifted towards the right side with
the increase of pressure. It is illustrated for his (N, N-diethylaminotroponeiminato)nickel(II) which
remains in an equilibrium between the tetrahedral and square planar configurations in the nonpolar
solyents. With the increase of pressure, the proportion of the square planar configuration increa:ses and
it is evident from the reduction of the observed magnetic moment with the increase of pressure. It
happens so because the tetrahedral form (3T I ) is paramagnetic while the square planar form I ) is eA
diamagnetic.
ry
ra
ib
yl
Fig. 8.26.3.1 Structure of bis(N, N-diethylaminotroponeiminato)nickel(II)
(c) Bis(salicylaldiminato)nickel(II) type complexes may remain in the equilibrium, square planar
m
~ tetrahedral, depending on the nature of substitution on the ligand. Bis(N-sec-alkylsalicylaldiminato)-
he
nickel(II) complexes are the well studided examples to illustrate the square planar ~ tetrahedral
equilibrium. Higher temperature favours the tetrahedral configuration and consequently the higher
lc
f.lobs is noticed at a higher temperature. When the cfse factor to stabilise the square planar isomer is only
marginally important, the system moves towards the tetrahedral isomer to get a better steric relaxation
ea
with the increase of temperature. Higher pressure favours the square planar configuration, i. e. higher
pressure leads to less Jlobs (cf. molar volume of the square planar isomer is relatively smaller).
th
H I
e/
N~/0:M-
-fQC
t.m
X Ni X
0 / """N=CH
I
R
e
Sis-complex of Ni(lI) with the N-substituted salicylaldimine.

er
The said square planar ~ tetrahedral equilibrium is supported by the spectral studies. In solution,
the peaks at 7,200 cm- 1 and 11,200 cm- I are the characteristic features of the tetrahedral complexes of
H
Ni(ll) while the peak at 16,000 cm- I indicates the presence of the square planar structure. With the
increase of temperature, the intensity of the peak at 16,000 cm- I decreases while the intensities of the
k
tetrahedral peaks (at 7,200 cm- I and 11,200 cm- I ) increase. It indicates that the tetrahedral isomer
lic
is thermodynamically more stable. It is probably due to the less steric effect in the tetrahedral com-
plex. The square planar complex looks olive green while the colour of the tetrahedral isomer is brown.
C
Because of the steric factor, the more bulky R group will favour the tetrahedral structure, Le. the
more bulky R group will lead to higher f.lobs.
Similarly, bis(2-hydroxy-I-naphaldiminato)nickel(ll) complexes also show this type of configura-
tion equilibrium.
CH=N-CHR2
OH
(2-hydroxy-1-naphthaldimine)
(d) The following Ni(II) complex also remains in an equilibrium between the square planar (dia-
magnetic) and tetrahedral (paramagnetic) structures in solution.
ry
ra
ib
yl
(R = tert-Bu, R1 = alkyl group)
m
Note: The closely related complex with the O-donor sites (i.e. S donor is replaced by 0 donor)
he
remains in the following equilibrium (cf Chern. Phys. Lett., 231, 235, 1994): "
Square planar (paramagetic, olive green) ~ tetrahedral (paramagnetic, dark blue)
lc
The unusual observation is that the square planar complex is also paramagnetic, i. e. high spin
square planar complex of Ni(II). The corresponding S-donor ligand is also a weak field ligand, but the
ea
favoured nephelauxetic effect favours the spin pairing through the reduction of pairing energy and
electron-electron repulsion measured by Racah parameter (B).
th
8.26.4 Octahedral-Tetrahedral Equilibrium (ct. Sec. 7.17.2)

e/
(a) [Co(acac)2] can maintain the octahedral ~ tetrahedral equilibrium where the octahedral coordi-
t.m
nation is attained through the polymerisation. This aspect has been discussed in Sec. 8.26.2 (cf Fig.
8.26.2.3).
(b) [Co(NCS)2(P-toluidine)2] can maintain the 0h ~ T d equilibrium where the octahedral
e
coordination is attained through the polymerisation. The complex when dissolved in DMF (dimethyl-
er
formamide which can act as a coordinating solvent) gives an anomalous magnetic moment (J.lobs = 4.88
B.M., cf J.lOh ::::; 5.0 B.M., J.lTd ::::; 4.6; Sec. 8.18.2) and two spectral peaks (intense band at
H
-15,870 cm- I and weak band at -19,800 cm- I ). The intense band is due to the tetrahedral complex
while the weak band is due to the octahedral complex. It is suggested that in DMF solution,
k
[Co(NCS)2(P-toludine)] produces [Co(DMF)4(P-toludine)2][Co(NCS)4]' i.e. octahedral cationic complex

and tetrahedral anionic complex. The magnetic moment is obtained as follows:
lic
J..I.;ty = aohJ..l.bh + <XrrdJ..l.~d; J.leff = 4.88 B.M.

C
Taking J.lOh = 5.2 B.M. and J.lTd = 4.5 B.M., we get UOh ::::; J.lTd ::::; 0.5 Le. 50 - 50 mixture.
(c) Thermochromism of (NRxH4-x)[NiCI 4 ] (x = 1, 2, 3) can be explained by considering the
temperature dependent octahedral ~ tetrahedral equilibrium. At the low temperatures, it looks yellow
brown or green due to the octahedral geometry attained through the bridging chloride ligands while at
the higher temperatures, it looks blue due to the tetrahedral coordination.
(d) Bis(N-methylsalicylaldiminato)cobalt(II) is tetrahedral but when dissolved in a noncoordinating
solvent, it may undergo dimerisation giving rise to the 5-coordinate cobalt centres. A similar situation
arises for the corresponding Ni(II) complex (cf Fig. 8.26.2.2).
8.27 ANOMALOUS MAGNETIC MOMENTS OF SOME FIRST TRANSITION METAL

COMPLEXES
Sometimes, f.!obs deviates from the f.!spin-only value and this deviation originates from the following
sources:
(i) orbital contribution from the ground state;
ry
(ii) orbital contribution from the excited state through the spin-orbit coupling and this may make
either a positive or negative contribution depending on the sign of spin-orbit coupling constant (A);
ra
(iii) contribution from the secondary Zeeman effect but this contribution is very often negligible.
ib
Thus orbital contribution either from the ground state (T-term) and excited state (T-term) makes f.!obs
different from f.!spin. It may be noted that the ground state characterised by A or E term cannot make any
yl
orbital contribution. Considering this factor, we can predict the expected value (i.e. range) of f.!obs and
m
this is called the normal range (cf. Table 8.27.1).
he
Table 8.27.1 Normal Range of magnetic moment (in B.M.) for Fe(III), Fe(II), Co(II), Ni(II) Complexes
Metal ion Octahedral 5-coordinate (C4v) Square Planar Tetrahedral
Fe(III), d S
lc
ea
High spin: ....5.9 -5.9 ....5.9
Low spin: -2.3 -1.9
th
Fe(II), d 6
e/
High spin: ....5.1 - 5.7 5.1 - 5.5 -5.4 5.0 - 5.2

Low spin: ....0
t.m
Co(II), d'
High spin: 4.7 - 5.2 4.2 - 4.6 4.2 - 4.8
Low spin: 1.8 - 2.0 1.7 - 2.1 2.1 - 2.8
e
Ni(II), d 8
er
High spin: 3.0 - 3.3 3.0 - 3.45 3.45 - 4.0

Low spin: -0 0
H
Sometimes, f.!obs deviates significantly from the normal range given in Table 8.27.1. This significant
k
deviation is referred to as anomalous magnetic moment.

lic
The origins of anomalous magnetic moment are:

(i) ferromagnetic interaction (for the magnetically concentrated substances)
C
(ii) antiferromagnetic interaction

(iii) thermal equilibrium between the spin states
(iv) configurational equilibrium leading to spin state equilibrium
(v) monomer-polymer equilibrium with the different stereochemistries and different magnetic moments
(vi) Solvent or anion coordination leading to the change in spin state
(vii) magnetically nonequivalent sites in the unit cell as in Lifschitz Salt
All the origins (iii) to (vii) have been discussed and illustrated in Secs. 8.24, 25, 26 and 8.27.
8.28 MAGNETIC EXCHANGE INTERACTIONS: SUPEREXCHANGE INTERACTIONS IN

TERMS OF GOODENOUGH-KANAMORI-ANDERSON RULES (GKA RULES)
8.28.1 Superexchange Phenomenon
Superexchange interaction leads to the magnetic exchange between the paramagnetic metal centres
through the orbital overlap of the diamagnetic bridging ligand atoms. Here the ligand filled orbital
ry
participates. The term superexchange was coined because this path can bring about the magnetic ex-
change interaction between the metal centres when placed at long distances (say, 300 - 500 pm).
ra
This superexchange interaction may lead to both the ferromagnetism and antiferromagnetism. For
the interaction between the spins 51 and 52 of two different magnetic centres (say 1 and 2), the exchange
ib
Hamiltonian (H) is given by Heisenberg-Dirac-van Vleck (HDvV) equation.
yl
1
H = -2J5152 , 51 = 52 = 2" ;2J = singlet-triplet energy gap, i.e. E(5 = 0) -E(5 = 1) = 2J, (el Sec.
m
8.31.1)
The coupling constant (1) is negative for the antiferromagnetic (AF) interaction (i.e. the spins are
he
paired) and J is positive for the ferromagnetic (F) interaction (i.e. the spins are parallel).
z
y
lc
ea
x x
th
e/
t.m
Pz Px Py
\.___________ __---------J
~
(a) Ligand p -orbitals
e
er
x y z
H
x
k
lic
dxy dyz dxz d3z 2_ r2 d x2_ y2

C
l J l == d z 2
~
J
~ eg
t2g
(b) Metal d-orbitals, in the octahedral crystal field; the ligand atoms are placed in the ±x, ±y and ±z directions.
Fig. 8.28.1.1 Schematic representation of the angular dependence of the metal d-orbitals and ligand p-orbitals involved
in the superexchange process.
Superexchange interaction is generally important in solid state lattice where the partially filled
metal d-orbitals are split into the t2g (i.e. dxy, dyZ' d xz ) and eg (d x2 _ y2 and d Z2 ) sets (cl Fig. 8.28.1.1) in
an octahedral crystal field. The involved ligand p-orbitals are PX' Py' Pz' In reality, the ligand uses the s-
P hybrid orbitals rather than the pure p-orbitals. For the sake of simplicity, here we shall consider the
participation of filled pure p-orbitals of the ligands.
8.28.2 Statement of the GKA Rule

(i) 90° superexchange leading to a F interaction: A strong antiferromagnetic (AF) superexchange
ry
interaction occurs when the partially filled d-orbitals of the metal centres interact at 180° bond
angle (i.e. magnetic ion-bridging ligand atom-magnetic ion angle = 180°).
ra
(ii) 180° superexchange leading to an AF interaction: The 90° superexchange (i.e. magnetic ion-
bridging ligand atom-magnetic ion angle = 90°) interaction leads to a weak ferromagnetic (F)
ib
superexchange interaction between the metal centres having the partially filled d-orbitals. Here
yl
the metal d-orbitals are interacting with the orthogonal ligand orbitals.
Note: Exceptions of these general statements will be illustrated later (cf. Fig. 8.28.3.6: 90°
m
superexchange leading to an antiferromagnetic exchange; Fig. 8.28.4.1a: 180° superexchange
leading to a ferromagnetic exchange).
he
8.28.3 GKA Rules in Terms of Overlap Integrals: Orthogonal and Nonorthogonal
Orbitals lc
ea
• Orthogonal orbitals: If two orbitals are orthogonal, then the overlap integral is zero. It leads to a
ferromagnetic exchange when the ligand and metal orbitals are orthogonal.
It is illustrated in Fig. 8.28.3.1. It can happen for (i) dxz (t 2g ) and Pz (Po); (ii) d.ry (t 2g ) and Px (Po);
th
(iii) d x 2 -y 2 (e g ) and Py (Pn)'

e/
x
t.m
x
e
---~-+---Et--~--Ir-----+--.
Z
x
er
H
k
lic
l. ) )
~ ~
(d xz- pz) combination ( d x2 _ y2 + Py) combination
C
Fig. 8.28.3.1 Orthogonal orbitals producing the zero overlap integrals leading to a ferromagnetic interaction.
• Po and Pn ligand orbitals: The ligand p-orbital whose axis points towards the metal centre is called
the po-orbital (characterised by the Coo symmetry element). The ligand p-orbital whose axis is perpendi-
cular to the line connecting the metal centre and ligand atom is called the Pn-orbital. Thus, an orthogonal
interaction arises in the following cases when the metal centre maintains the octahedral symmetry:
and Po; eg and Pn i.e. t 2g ..L Po and eg ..L Pn where ..L stands for the orthogonality.
t 2g
• Nonorthogonal orbitals: If two orbitals are nonorthogonal, and they can produce a reasonably high
overlap integral, then it leads to an electron transfer or a partial covalence. This leads to an
antiferromagnetic exchange. It happens so when the ligand and metal orbitals are nonorthogonal. It
is illustrated in Fig. 8.28.3.2 for (i) d Z2 andp z (Po) ; (ii) d x2_y2 and Px (Po); (iii) dxy and Py (Pn)'
Thus the nonorthogonal interactions arise in the following cases:
eg and Po (i.e., eg '1... Po); t2g and Pll (i.e., t 2g '1... Pll)
ry
( ~ stands for nonorthogonality)
ra
• Anti-ferromagnetic exchange for a finite overlap integral: This may be attained in the follow-
ing cases for an octahedral coordination around the metal centre.
ib
(i) eg orbitals projected directly towards the ligand orbitals in 180 0 superexchange i.e., interaction
yl
of the Po orbital of the ligand with the eg orbitals of the metal centres: It is illustrated below.
m
p; (L) - d~2 (M
{
d~2 (M 1) - 2) (180 0 superexchange)
he
Figs. 8.28.3.3-4
d~2_y2 (M 1) - p; (L) - d~2_y2 (M 2) (180 0
superexchange)
lc
ea
x
th
e/
z
t.m
----.......---_--------J
l.
e
(d Z
2 - Pz) combination
er
H
y y
y
k
lic
x ---~ .....~-~-.. x
C
Px
) ---v-
--.........---- ( dxy + py) combination
( d x2_ y2 - Px) combination
Fig. 8.28.3.2 Nonorthogonal orbitals producing the nonzero overlap integrals (i.e. covalence) leading to the charge
transfer and an antiferromagnetic interaction.
ry
z
ra
ib
2
d/ pz dZ
yl
\..... ~ __- - - - - - - - - - - - J
~
m
AF interaction
(d/ - pz - dZ2 ) combination
he
lc
Fig. 8.28.3.3 Schematic representation of 180 0 sUPerexchange interactioQ itt d;2 - p; - d ~2 combination leading to an
ea
antiferromagnetism.
th
-,,\
y y
e/
t.m
---+-----""'*"---_+_~+----...-;lJf----_+_r_+---~Wr_----_+---. X
e
er
Spin pairing
H
AF interaction
k
l________ Px _-------.J
lic
~ AF interaction
C
Fig. 8.28.3.4 Schematic representation of 180 0 superexchange interaction in (d.~2 _),2 - p; - d~2 _),2 ) combination leading
to an antiferromagnetism.
(ii) t 2g orbitals participating in 180° superexchange with the Pn orbitals of the ligand: It is illustrated
below.
(180° superexchange)
y
Spin pairing
AF interaction
ry
ra
ib
yl
m
l J
he
( d xy + Py - d xy ) combination (Antiferromagnetic exchange)
lc
Fig. 8.28.3.5 Schematic representation of 180° superexhange interaction in (d~ + p; - d~) combination.
(iii) the eg orbital of one metal centre participating in 90° superexchange with the t2g orbital of
ea
another metal centre: It is illustrated below.
d~2 {Md - p; (L) - d~z (M

th
2 )} 90° superexchange (Fig. 8.28.3.6)

e/
x
x
t.m
Po towards
dz' (a g) )
e
+
er
---+------~~-----+-,J......fo-----"*_------_+_--__.z
H
spin-pairing
k
z
lic
C
dz 2~
(0)
PZ ~d
(1t) xz
( dZ 2 - pz - dxz) combination; leading to an antiferromagnetism
Fig. 8.28.3.6 Schematic illustration of 90° superexchange in d~2 - p; - d;z interaction leading to an antiferromagnetism.
Here, the Pz ligand orbital acts as a Po orbital towards the d Z2 (M.) orbital while it acts as a Pn orbital
towards the dxz (M2) orbital.
The overlap integral in both t2g- P1t bond and eg- Per bond is nonzero. But, the t 2g - P1t bond is
weaker than the eg - Per bond. Because of the nonzero overlap integral, the overall interaction is '
antiferromagnetic. It may be noted that this 90° superexchange leads to an antiferromagnetism (Fig.
8.28.3.6).
ry
ra
ib
yl
z
m
he
l
Ferromagnetic
lc -..y-
Antiferromagnetic
ea
L )
~
l Ferromagnetic
~
th
(a) (d~z 1- P~ ~ d~2) combination (cf. 180 superexchange

0
e/
but ferromagnetic exchange)

t.m
e
er
H
---+----~~----~~----A-------+-------+x
k
lic
C
d X2_ y 2(e g) ~ ~ ( )
Ferromagnetic Ferromagnetic d x2_ y2 eg
l
~
l. Antiferromagnetic )
--------~----------
(d :2_ y2 1- P: (py) 1.. d :2_ y2) combination
(b)
x x x
ry
ra
z
ib
yl
m
Ferromagnetic Ferromagnetic
he
l. J
~
L A_n_tiferromagn_et_ic-------J
lc
~1
ea
d xz (~) Pz (~) dxz
(c)
th
Fig. 8.28.4.1 Some representative examples of orthogonal and nonorthogonal orbitals in 180 0 superexchange.
• Ferromagnetic exchange in the case of zero overlap integral: This aspect will be discussed and
e/
illustrated later.
t.m
8.28.4 Orbitals Involved in 180 and 90 Superexchange Interactions

0 0
(i) Orthogonal and nonorthogonal orbitals in 180° superexchange.

t2g(Ml)1-Po(L)1-t2g(M2)' e.g., d xz 1-p z 1-dxz (cf. Fig. 8.28.4.1c)
e
eg (M 1 ) ~ Po (L) ~ eg (M 2 ), e.g., d Z2 ~ Pz ~ d~2 (cf. Fig. 8.28.3.3)

er
Antiferromagnetic
eg (M 1 )1-p1t(L)1-e g (M 2.) , e.g., d X2 _y2 1-p y 1-dx2 _y2 (cf. Fig. 8.28.4.1b) interaction
H
t 2g (M 1 ) ~ P1t (LY~ t 2g (M 2 ), e.g., d xy ~ Py ~ d xy (cf. Fig. 8.28.3.5)

k
M)
'\I ( ) '\I
eg M 2 ,e.g., dx- 1- p.. -.h.. d 2 cf· FIg. 8.28.4.1a
(. )} Ferromagnetic
· t t.
1 1- Po L
t2 ( () -.h..
In erac Ion
(J
lic
~ " " z
(ii) Orthogonal and nonorthogonal orbitals in 90° superexchange.
t 2 g (M I ) 1- P (L) ~ t 2 g (M 2 ), e. g., d;n' 1- Px ~ dxv
C
(1t) .
. (0)
eg(Ml)~p(L)1-eg(M2)' e.g., d..2 ~pz 1-d 2

"(0) (1t) z
eg (M 1 ) 1- p(L) ~ eg (M 2 ), e.g., d 72 1- Px ~d72
,,(1t) (0)"
(cf. Fig. 8.28.4.2)
t 2g (M 1 ) ~ p(L) 1- t 2g (M 2 ), e.g., d xv ~Pv 1- d xv
. (1t) . (0) .
eg (M 1 ) ~ p(L) ~ t 2g (M 2 ), e.g. d 2_,2 ~ Px .1. d xv
x .\ (0) (7t) .
eg (M 1 ) 1- p(L) 1- t 2g (M 2 ), e.g., d 72 1- Px 1- d xz
~ (1t) (0-)
y
y
(cr - interaction
F-e:Change) )
ry
+
X
ra
ib
yl
X
m
he
(d~y+ P: + d;y) combination (Ferromagnetic exchange)
(1t)
lc
(a) dxy ..L Px ':i. d xy (c/.dxy ':i.P y ..L dX),)
(0) (1t) (0)
ea
[cf e~ (0)
'l. p 'l. t~g e.g. d 2 _ 2 'l. P; ~ d~, (90 0 snperexchange) lead's to an antiferromagnetic
2 1
(1t) x y (0) (1t)
th
exchange; c/. Fig.8.28.3.6]

X
e/
(It - interaction) ~
t.m
e
er
z
H
k
lic
C
dZ 2
(Ferromagnetic exchange)
y y
ry
x
ra
ib
x
yl
m
he
(Ferromagnetic exchange)
(Case of accidental orthogonality
of the dX 2_ / orbitals) lc
ea
(c) d
X
2 ~ Px (1t)
-y 2 (cr) 1- d x2 -y 2 (c/. d x
2 2
-y (1t)
~ d x-y
1- P,..' (cr) 2 2 )
th
x
e/
Px
t.m
e
---+-----~ .......----~~-----------. z
er
o towardsd xz
H
dZ 2 Ferromagnetic
k
exchange
}
lic
----~ ......~---------- ... z

C
(Antiferromagnetic
exchange)
d/(~) Px (~) d xz
(d) (d~2 + P; + d~z) combination; zero overlap integral for P1t - d Z2 interaction and Pcr - d xz interaction
Fig. 8.28.4.2 Schematic representation of orthogonal and nonorthogonal orbital interaction in 90° superexchange.
Summary of the GKA rules
• t 2g ~ P1t ' eg 'l. Pcr (nono~thogonal, i.e. nonzero overlap integral)

~ covalence, charge transfer, antiferromagnetic interaction
• Nonorthogonality attained through the a-interaction is stronger than that attained through
the 1t- interaction
ry
• t 2g 1.. P cr and eg 1.. P1t (orthogonal, i.e. zero overlap integral)
ra
~ ferromagnetic interaction
ib
8.28.5 Magnetic Exchange Interaction (180°) in Some Representative Compounds
yl
in Terms of GKA Rules
(a) CaMn03: In this mixed oxide, the magnetic centre Mn 4+ (3d3 ) is having the octahedral coordination
m
i
(i.e. t2 e~). Here the 1800 superexchange interaction arises through the participation of the filled
p-orbitals of 0 2-. The filled Px' Py and Pz orbitals of 0 2- are of two types:
he
Po (the axis of the p-orbitallies along the Mn-O bond)
P1t (the axis of the p-orbitallies perpendicular to the Mn-O bond)
lc
ea
th
e/
t.m
2 •••.• ~t:,g
Po
e
er
O 4+ .i p2 2- 1. t1 4+
e9 (Mn).. • 0 (0 ) 4 . ~ 29 (Mn )
charge ferromagnetic
H
transfer
1+ ~ + --------9------+
-lerroma- netic- - - . ~
antiferromagnetic
k
lic
Fig.8.28.5.1 Schematic illustration of 1800 [Mn4+... pcr(02-) ...Mn4+] superexchange leading to an antiferromagnetic
interaction (e~ (M t ) ~p~ -it: (M 2 ) e.g. d~2_i ~p; -id~ ) in CaMn0 3 .

C
1I
Here the antiferromagnetic superexchange interaction can be attained in different possible paths.
These are discussed here.
(i) eg - pJ0 2-) - 12g 180 a-type superexchange path: The ligand Po orbital is nonorthogonal ('1..) to
0
the e g orbital and they can overlap to produce a covalent bond. In this interaction, the charge transfer
from the Po orbital with the upward spin occurs to the eg orbital (which is already remaining fully
vacant). This charge transfer with the upward spin is according to the Hund's rule of of maximum
multiplicity (cf. 3 unpaired t2g electrons are already with the upward spin). This parallel orientation of
the spins enjoys the exchange energy. This nonorthogonal overlap with the vacant eg-orbital actually
establishes a 2c-le covalent bond (described as semicovalent bond) which in other words leads to the
said charge transfer to the eg-orbital. The remaining Po orbital electron with the downward spin makes
an orthogonal overlap with the t2g orbital (which is already half-filled as t2~ i.e. 3 unpaired electrons
with the upward spin) of another Mn 4+ centre. This orthogonal interaction leads to a ferromagnetic
interaction (i.e. both the Po electron and t2g electron remain with the downward spin). Thus the
resultant superexchange interaction between the Mn4+ centres is antiferromagnetic, i.e. the up-
ry
ward spin in (M 1) is antiferromagnetically coupled with the downward spin in (M2) (cf. Figs.
8.28.5.1-2). The eg ':i. Po ..1 t 2g 180 superexchange interaction is illustrated in Fig. 8.28.5.2a.
ra
0
ib
yl
m
he
x
Px
lc
ea
Ferromagnetic
th
exchange
e/
(d~2_ y2 - P~+ d~), i.e. e~ - P: + t;g combination

t.m
dx _
2
y2 (~ Px (~) dxy
Fig. 8.28.5.2a Schematic representation of 1800 superexchange in d~2_l ~ p; 1- d;y leading to an anti-
ferromagnetic exchange.
e
This 180 superexchange orients the t2g electrons downward at one Mn(IV) centre and upward at
0
er
the other Mn(IV) centre to bring about the antiferromagnetic interaction (cf. Figs. 8.28.5.1-2).
(ii) t~g - pcr(02-) - t~g a-type 1800 superexchange path: The following a-type 180 0 ;uper-
H
exchange path also brings about an antiferromagnetic interaction.

k
1
t2g~P
(1 2 ( 2-)
0 1
~t2g,e.g.,
(1 l
d xz~Pz
(1 2 ( 2-)
0 ~
(1 l
d xz f FIg.
(c. . 8.28. 4. 1c.)
lic
(iii) eg - Pa(02-) - eg 180 0 a-type superexchange path: Besides the above mentioned paths, the
C
0
a-type 180 superexchange path e~ ~ p~ ~e~, e.g. d~2_y' - p; - d~2_y combination can also bring
about the antiferromagnetic interaction. One electron transfer from the p (12 orbital to a d x 2 -y 2' orbital
will occur with the upward spin according to Hund's rule (assuming the ~g electrons remaining with the
upward spin). Transfer of the remaining po-electron (of the bridging 0 2-) with the downward spin will
occur to the d x 2 -y 2 orbital of the other metal and it will direct the ttg-electrons to be oriented with the
downward spin according to Hunds rule. It is illustrated Fig. 8.28.5.2b. This superexchange path orients
the t 2g electrons with upward spin at one Mn4+ centre and with downward spin at the other Mn4+ centre
to bring about the antiferromagnetic interaction.
Q)
Q) ~
- 0
::J_
Semicovalance or ;;; Q)
Charge -
\Jc:C)
.1 transfer I
c: tl3
::J.r;,
===::j:~~? .... ~~:::::;...~~:.==

IU x
~
x
""'-1 l;"" •
ry
]1 ::::PI~L~=J
ra
p:(d-)
1~
ib
Antiferromagnetic
yl
(orbital picture
exchange
of overlap)
m
Fig. 8.28.5.2b Antiferromagnetic interaction between the metal centres (t~g) through the transfer of each 2p electron of
oxygen to the vacant eg orbitals of the metal centres (i.e. each 2Pcr -electron of oxygen forms a 2c - Ie semicovalent bond
he
with each metal centre).
(iv) t 2g - p1t(02-) - t 2g 180 0 x-type superexchange path: Here it may be mentioned that the lc
t~g (Mn 4+) ~ P; (0 2
- ) ~ t~g (Mn 4+) 180 0 1t-type superexchange interaction (cf. Fig. 8.28.5.3)
ea
can also bring about the antiferromagnetic interaction. In Fig. 8.28.5.3, it is illustrated for the
d~ (Mn 4+) - P~ (0 2-) - d~, (Mn 4 +) interaction.
th
y
Spin pairing Y Y
e/
AF interaction Spin pairing

,----"--, AF interaction
t.m
e
er
H
k
lic
l _ )
C
~
1 2 1. 1 2 1 ..
(d xy + Py - dxy ) I.e. t2g + Pn - t2g combination
Fig. 8.28.5.3 Illustration of 180 0 superexchange (1t-type) interaction leading to an antiferromagnetism.
Here it may be mentioned that the t 2g - P1t interaction is much weaker than the eg - Pa and t 2g - Pa
interactions. This is why, the antiferromagnetic interaction attained through the pJ orbital of 0 2- is
more important than the pathway involving the p; ~rbital of 0 2-.
(b) MoO (cf. Sec. 8.32.8): In this oxide, the magnetic centre Mn 2+ (d5) is having the octahedral
coordination (t2~ ei, i.e. high-spin state). The filled p-orbitals (both Po and Pn) of 0 2- can bring about
the antiferromagnetic interaction through the 180° superexchange. The important superexchange path-
ways are discussed here.
(i) e~ - p~ (0 2 - ) - e~ 180 a - type superexchange path: Let us first illustrate the participation of
0
the Po orbital in the e~ (Mn 2+) ~ p~ (0 2- ) ~ e~ (Mn 2+) 180° a-type superexchange path, e.g.
ry
d~2 ~p; ~d~2' d~2_y2 ~ P; ~d~2_y2 (cf Figs. 8.28.3.3-4). This is schematically illustrated in
ra
Fig. 8.28.5.4.
Here the nonorthogonal interaction of the ligand Po orbital with the half-filled eg-orbital of one Mn 2+
ib
centre leads to the charge tranfer (the downward spin from the Po orbital to the half-filled eg erbital
of Mn 2+) and the remaining Po orbital electron with the upward spin participates in a nonorthogonal
yl
interaction with the half-filled eg orbital of another Mn 2+ centre. It gives the resultant antiferromagnetic
interaction between the Mn 2+ centres. The orbital overlap model is shown in Fig. 8.28.3.3-4.
m
(ii) t~g - p~ (0 2 -) - t~g a-type 180° superexchange path: The following a-type 180° super-
he
exchange path also brings about an antiferromagnetic interaction.
lc
tig ~ p2 (0 2- )~tig, e.g. d~z ~ p; (0 2- )~d~z (cf Figs. 8.28.4.1c, 8.32.8.1).
ea
th
e/
t.m
4
e
er
~
H
1 2+
4 ~ eg(Mn )
charge antiferromagnetic
k
transfer
lic
~ +-------------~ ~
C
Antiferromagnetic ",,,,,..
... -
--- --- ---
Aniiferromagnet~-
Fig. 8.28.5.4 Schematic illustration of 1800 [Mn 2+... Po (02-) ••• Mn 2+] superexchange leading to an antiferromagnetic
interaction in MnO (cf. Figs. 8.28.3.3-4 for the pictorial representation of orbital interaction).
(iii) t~g - p~ (0 2 - )- t~g 1t- type 180° superexchange path: The 1t-bonding pathway,
i.e. tig (Mn 2+) ~ p; (0 2-) ~ tig (Mn 2+) 180° superexchange, e.g. d~ + p; - d~ (Fig. 8.28.5.3) can
also bring about the antiferromagnetic interaction between the adjacent Mn 2+ centres. This is illustrated
in Figs. 8.28.3.5, 8.28.5.3.
(c) NiO: The electronic configuration of Ni(II) in the octahedral crystal field is t2~ ei. The 1800
l
e g (Ni
2
+) 'l.. P: (0 2 -) 'l.. egl (Ni 2+) superexchange pathway, e.g.
v
l
d 2
Z
~Pz2 ~dI2;
Z
l
d 2 2
x -y
~px2 ~d12
x -y
2
can bring about the antiferromagnetic interaction between the adjacent Ni(II) centres. This aspect has
ry
been illustrated in the case of MnO (cf Figs. 8.28.3.3-4, 8.28.5.4).
ra
Here it is worth mentioning that the n-bonding pathway is not relevant because there is no unpaired
electron in the t 2g level. Because of the same ground the t 2g -PJ.0 2-) - t 2g a-type 180 0 superexchange
ib
pathway is not applicable here though the pathway works in MnO.
(d) Mixed oxide of Fe(III) and Cr(III) having the bridge FellI - 0 - ll
Cr
: In the weak octahedral
yl
crystal field, the electronic configurations are:
m
Cr(III): t2~ e~; Fe(III): t2~ ei;
The e~ (Cr 3+) ':1. p~ (0 2 -) ':1. e~ (Fe 3+) e.g. d~2 (cr 3+) ':1.p~ ':1.d~2 (Fe 3+) 1800 superexchange path-
he
way can lead to a ferromagnetic interaction. It may be noted that though it is a 180 0 superexchange
lc
path, it leads to a ferromagnetic interaction. The cr3+ - Pcl02-) - Fe3+ superexchange path is
illustrated in Fig. 8.28.5.5 (see Figs. 8.28.3.3-4 for an orbital overlap interaction).
ea
The nonorthogonal interaction between the Po orbital and the eg orbital of Cr(III) leads to the charge
transfer. This charge transfer with the upward spin occurs to the vacant eg orbital of Cr(III) according
th
to the Hund's rule of maximum multiplicity. The remaining Po orbital electron with the downward spin
undergoes a nonorthogonal overlap interaction (cf Figs. 8.28.3.3-4) with the half-filled eg orbital of
e/
Fe(III). This nonorthogonal interaction leads to an antiferromagnetic interaction. But the overall
superexchange interaction between the Cr3+ and Fe 3+ centres in this route is ferromagnetic.
t.m
e
er
H
3
k
~g
lic
. p~(02-) ~ e~
C
~ ~
.. • (Fe3+)
charge
antiferromagnetic
transfer
1......
--- --- --------------- --- -_ ....
Ferromagnetic
Fig. 8.28.5.5 Ferromagnetic 1800 superexchange interaction between cr3+ and Fe 3+ i.e. e~ (Cr 3+)- p~ (0 2 - )- e~ (Fe 3+).
Here it is worth mentioning that the 180 0 x-bonding superexchange pathway, i. e.

tig (Cr +) ~ p~ (0
3 2
-) ~ tig (Fe 3+), e.g. d~ (Cr 3+) + P~ - d~ (Fe 3+) brings about the antiferro-
magnetic interaction (cf Figs. 8.28.3.5, 8.28.5.3) between Fe 3+ and Cr3+ centres. But the n-bonding
pathway (i.e. t2g - Prr) is less important than the a-bonding pathway (i.e. eg - Pcr). This is why, the
resultant effect is a ferromagnetic interaction between the Fe3+ and Cr3+ centres.
ry
In the same way, it can be shown that the 180 0 e~ (y2+) ~ p~ (0 2-) ~ e~ (Ni 2+) superexchange
ra
leads to a ferromagnetic interaction between y2+ (t2~ e~) and Ni 2+ (t2~ ei).
ib
8.28.6 Magnetic Exchange Interaction (90°) in Some Representative Compounds in
Terms of GKA Rules
yl
(a) NiCI 2 : It adopts the CdCI 2 type structure where the anions (CI-) are distributed in a ccp pattern
m
in which half of the octahedral holes are occupied by the cations Ni 2+. This can be attained in two ways:
(i) half of the octahedral holes in each layer can be occupied by the cations, i.e. Ni 2+ ions;
he
(ii) all the octahedral holes in each atternate layer can be occupied by the cations, i.e. Ni 2+ ions.
In the CdCI 2 type structure, the second possibility is attained, i.e. all the octahedral holes in each
lc
alternate layer are occupied by the bivalent cations. Thus, a sheet of M 2+ ions is sandwiched between
ea
the adjacent layers of anions. The anions of one layer adjacent to those of the next layer are' held
through weak van der Waals forces. The examples are: MCl 2 (M = Mn, Fe, Co, Ni).
Thus in the CdCI 2 type structure, M 2+ ions are sandwiched between two layers of the anions, i.e.
th
el- ions (see Sec. 11.13, Yol. 2). It can produce 90 0 M 2+- CI-_M 2+ superexchange interaction for the
e/
anions present in a particular layer but it cannot produce a 180 0 superexchange.

t.m
e
P2(CI-)
er
6
1(iL
4& 4& 1(iL2
t29
H
2
(Ni +) (Ni +)
k
CI ~ ..L
e~(Ni2+) 4
lic
~ p2(cr) 4
NM<Ni charge
transfer
ferromagnetic
C
1~ I'+----------- .. ,
ferromagnetic
........... ",,,,~
--- ---
Ferromagnetic
Fig.8.28.6.1 Schematic representation of 90° Ni 2+ - p(CI-) - Ni 2+ superexchange leading to a ferromagnetic interaction

between the, Ni 2+ -centres. Note: For the pictorial representation of orbital interaction, see Figs. 8.28.4.2b, c.
Note: The orbital interaction is: e g (Ni 2+ ) ~ p (Cl- ) -L e g (Ni 2+ )
(0) (rr)
In fact, the edge shared octahedrons can only allow the 90° superexchanges. Ni 2+ maintains the
octahedral coordination with the electronic configuration: t2~ ei.
The filled p-orbitals of CI- participate
in the superexchange interaction. The p2 orbital being nonorthogonal (a-type overlap) to the eg orbital
of Ni 2+ can produce a partial covalence with the e~ orbital of Ni 2+. This will lead to charge transfer from
the Pcr orbital with the downward spin to the eg orbital of Ni 2+ where already the upward spin is existing.
Then the remaining p-orbital electron with the upward spin makes an orthogonal7t-type overlap (90°
ry
superexchange) with the e~ orbital of another Ni 2+ centre (cf. Figs. 8.28.4.2b, c).
Representative examples of such 90° superexchange paths are: e~ (M 1 )-t p 2 ':1..e~ (M 2 ), e.g.
ra
d~2 (*)P; (*)d~2' d~2_l (*)P; (*)d~2_l (c/. Figs. 8.28.4.2b, c). This leads to a ferromagnetic
ib
coupling. The resultant superexchange interaction between the Ni 2+
centres is of ferromagnetic type.
yl
This is illustrated in Fig. 8.28.6.1.
(b) MnCI2 : It also adopts the CdCI2 type structure. The 90° Mn2+ - CI--Mn 2+ superexchange
m
interaction is illustrated in Fig. 8.28.6.2. The electronic configuration of octahedral Mn2+ (high spin) is t2~
ei.
he
The p2(CI-) orbital can make a nonorthogonal7t-type overlap with the t2g orbital. This overlap produces
a partial covalence leading to the transfer of charge with the downward spin from the p orbital of CI- to
the half-filled t2g orbital of Mn2+. The remaining p(CI-) orbital electron with the upward spin undergoes a
lc
nonorthogonal a-type overlap with the half-filled eg orbitals of Mn2+. This nonorthogonal overlap (i.e.
ea
nonzero overlap integral) produces an antiferromagnetic interaction (cf. Fig. 8.28.3.6). The resultant
superexchange interaction e.g. d~2 (Ml)(~P~ (CI- )(~d~z (M 2 ) (c/. Figs. 8.28.3.6), between the Mn2+
th
centres is of antiferromagnetic type. (cf. Figs. 8.28.3.6, 8.28.6.2)

e/
t.m
e
93
er
H
k
lic
~ (0)
~ e~ (Mn +)
2
lIII
antiferromagnetic
C
I +------------------. ~
antiferromagnetic
'" '" ",,,,)If
",'"
--- -----------------
Antiferromagnetic
Fig. 8.28.6.2 Schematic representation of 90° Mn 2+-p(CI-)-Mn2+ superexchange leading to an antiferromagnetic

interaction between the Mn 2+ centres. (cf. Fig. 8.28.3.6 for pictorial representation of orbital interaction).
Here it is worth mentioning that the following 90° superexchange (e.g. d~2_l ~p; l..d~2_l ) leads
to a ferromagnetic interaction between the Mn 2+-centres.
e1 (Mn2+)~(_ _~_(_cr)_ _----t)p2(CI-)~(__-l_(1t_)_~)egl (Mn 2+).
g Charge transfer ferromagnetic
(with downward spin)
ry
1 +-------------+ 1
ra
1~ . ferromagnetic
---
ib
--- ----------------- ---
yl
Ferromagnetic
m
This aspect has been already illustrated in Fig. 8.28.6.1 for NiCl 2 (cf Figs. 8.28.4.2b, c for the orbital
picture).
he
(c) CrC)3: The CI- ions (i.e. anions) are distributed in accp pattern as in CdCl 2 structure and 1/3rd
of the octahedral holes are occupied by the cations, i. e. Cr3+ ions. It is attained by filling the 2/3rd of
lc
the octahedral holes in the alternate layers by the cations. In the octahedral crystal field, the electronic
i e~. The 90° superexchange through tig (Cr 3+)} p2 (Cl- ) ~e~ (Cr 3+)
ea
configuration of Cr(III) is t2 is
illustrated in Figs. 8.28.6.3 and 8.28.3.6.

th
o __ __ ~
e/
e9 --.&+4---
~""""'"
~
C>
Q) ...
t.m
-0> I
::::s c:
a:w
en C>
..
0>
"c: "1
~
c: tU
::::SL:,
J: U
x """"
~~~
e
~ P2(CI-)
"A - - -+1--
er
--4 4- - - t2~
3
(Cr +)
H
oil ~ • t2~ (Cr +)

3
antiferromagnetic
k
lic
1
.......
C
--- ------------------- --- ---

Ferromagnetic
Fig. 8.28.6.3 Schematic representation of 90 0 e~ (Cr 3+) ~ p2 (CI-) ~t~g (Cr 3+) superexchange leading to a
ferromagnetic interaction between the metal centres (cf Fig. 8.28.3.6 for pictorial representation of orbital interaction).
1 ~(cr) 2 () ~(1t) 1 () 1 ( ) cr 2 1t 1 ( )
Note: eg ( Charge transfer ) p L ( Charge transfer )t 2g M 2 ,e.g. d Z2 M 1 -Pz - dxz M 2 leads to
an antiferromagnetic interaction (cf Figs. 8.28.3.6 and 8.28.6.2).
(d) CuCI2 : Here, the bridging halides produce the one dimensional chain lattice in which Cu(II)
maintains the square planar coordination. The bridging CI- ions share the adjacent square planar moieties.
ry
ra
The Cu 2+ centre experiences a tetragonal crystal field giving rise to the following electronic
configuration.
ib
yl
i.e. the unpaired electron resides in d x 2 -y 2. The CI- ions are placed along the lobes of d x 2 -y 2 orbital.
m
The 90° superexchange (d x2 -
l f ~ p2 {Cl-)..l (d l f X2 _ is illustrated in Figs. 8.28.4.2(c) and 8.28.6.4.
he
It leads to a ferromagnetic interaction between the Cu(II) centres.
(e) CoCI2 : It adopts the CdCI 2 type structure. The electronic configuration of Co(II) in the octahe-
dral crystal field of CI- ions is: t2~ ei lc
2+) e.g. d~ (Co 2+) + p; + d~ (c02+) superexchange leads
ea
The 90° t
2g
(Co2+)~ p{Cl- )~t2(Cog ,
to a ferromagnetic interaction between the Co2+ centres. This is illustrated in Figs. 8.28.4.2(a) and
th
8.28.6.5. The 90° superexchange path, e (Co2+)~ p{CI- )~eg (Co 2+) (illustrated in Fig. 8.28.6.1)
g
e/
can also bring about the ferromagnetic interaction.

t.m
b: g
--~1"""~-~-""" ~~~~~~-.;-.;..-~1-- b:g
i.e. (d x
'- y,)1
b29'-----..1+.-~ - - "" .;.;.; 1~ b29

e
"""" 4~.;.;.;.;.;.;
er
2
a1~y ---£fo1....~--
H
e; =~1;:;~=~1~c===
2
k
(Cu +)
lic
..L (1t)
.. ~ (b 19 )1
charge
C
ferromagnetic
transfer
Ferromagnetic
Fig. 8.28.6.4 Schematic representation of the ferromagnetic interaction through 90° superexchange in CuCI 2 • [et Fig.
8.28.4.2(c) for the pictorial representation of orbital interaction.]
41
ry
ra
~(1t) -.L (0)
ib
1 2+ 2
t2g (CO ) lIII ~ P (CI-) .lIII-----.~
yl
charge ferromagnetic
transfer exchange
(AF exchange)
m
1 +-------------+ 1
he
ferromagnetic
~""""
--- ------------- lc --- ---
Ferromagnetic
ea
Fig. 8.28.6.5 Schematic illustration of 90° C0 2+-p (CI-)-C0 2+ superexchange in CoCI 2 • (cf. Fig. 8.28.4.2a for the
pictorial representation of orbital interaction).
th
( t) N I·2+ -Po
0 2 1t C 3+
- ~ 2 (1t)t
r 90° superexchange: The superexchange process,_ e g1 ( Nl'2+) (cr)p ~ 1 (
C-1+
r),
2g
e/
e.g. d~2 - p; - d;z leads to an antiferromagnetic interaction between Ni 2+and cr3+. This is illustrated
t.m
in Figs. 8.28.3.6 and 8.28.6.6.
e~ ---'4r--+1~l- -
e
~"""
er
................~~----
P 2(0~) ----------- --h
H
==4-:'~;==1
1
=jt:===== t
3
2g
k
(Cr 3+)
lic
~
.lIII---- P
2(02-)
lIII
~ 1
~ t 2g (Cr )
3+
C
(0) (1t)
(charge transfer) (antiferromagnetic)
1~ ~ +----------. ~
(antiferrOmagne~~~~"
~""""""
--- ------------ ---
(Antiferromagnetic)
Fig. 8.28.6.6 Schematic illustration of 90° superexchange ei(Ni 2+) - p2(02-) - t2~(Cr3+) leading to an antiferromagnetic
interaction between Ni 2+ and cr3+. (cf. Fig.8.28.3.6 for pictorial representation of orbital interaction)
8.28.7 Ferromagnetism in Copper(II), Oxidovanadium(IV), and Oxidomolybdenum(V)

Complexes
It is evident that e~ + p2 ( L ) + t~g , e.g. d~2 - p; - d~z 90° superexchange (cf Fig. 8.28.3.6)
can produce the antiferromagnetic exchange, but e~ + p2 (L)~e~ 90 soperexchange (ef

0
ry
Fig. 8.28.4.2 b, c) can produce the ferromagnetic exchange. In the Cu(II)-complexes, the unpaired
electron resides in d x2 _y' (an ex orbital), thus the said 90 superexchange path, i.e. d~2_y' - p; + d~2_y'
ra
0
(cf Fig. 8.28.4.2c) can bring about the ferromagnetic coupling. In fact, a large number of ferromagnetic
ib
Cu(II) complexes are known.
yl
For the VO(IV) or MoO(V) complexes, the unpaired electron resides in the dxy orbital (a t 2g orbital).
Consequently, ferromagnetism in their complexes through the e~ + p2 (L)~e~ path (90 0
m
superexchange) cannot be attained. However, very weak ferromagnetic interaction through the path,
+
he
t~g p2 (L)~ t~g 90 0 superexchange d~ + p; + d~ (ef Fig. 8.28.4.2a) can be attained. In
this path, the nonorthogonality (~) leading to a covalence is attained through the n-bonding while in
lc
the 90 0 superexchange path e~ + p2 ( L ) + e~ which is possible for the Cu(II) complexes, the
ea
nonorthogonal orbital interaction is attained through the a-bonding which is much stronger than
n-bonding. This is why, in the oxovanadium(IV) or oxomolybdenum(IV) complexes, the
th
ferromagnetic interaction is rarely found. Moreover, the 180° 1t-type superexchange path, i.e.
p; -
e/
d~ + d~ (cf Fig. 8.28. 5.3) can bring about the antiferromagnetic interaction between VO(IV)
or MoO(V) centres.
t.m
8.29 INTERPRETATION OF MAGNETIC EXCHANGE AND GOODENOUGH-KANAMORI-

ANDERSON RULES (GKA RULES) IN TERMS OF MULTICENTRED MOLECULAR
ORBITALS FORMATION
e
8.29.1 Molecular Orbital Approach for the 1800 Superexchange Interaction

er
A. Involvement of eg orbitals and ligand Po orbital: Let us first illustrate for the e~(M) - p;(L) -
d; orbitals and one ligand Pz orbital of the bridging atom,
H
e~(M) 180° superexchange. For the two metal

we can have the combinations as shown in Fig. 8.29.1.1.
k
x x
lic
C
+
z
Pz (L)
Bonding a-Me (ep..): d Z2 (M) - pz (L) - d Z2 (M)
Nonbonding a-Me (~): d Z2 (M) + pz (L) + d Z2 (M)
Antibonding a-Me ('1»3): d Z2 (M) + pz (L) - d Z2 (M).

S = 1 (Triplet)
d/ ' dz 2
NBMO"\
=I P ~~E I
"
\
<1>2
\
\
\
\
J 2J
ry
\ \
\ \ cf. Fig.8.31.1.1
\ \
\ \
\ \
ra
\ \
\ \ I
r - -rule:
GKA --- --
180 - - - - - - . \"
0
superexchange ",,,,,,,,,,,,,,,, ,~ ,~"''''\'--1++17-r---- S = 0 (Singlet)
ib
producing an antiferro- " Pz
magnetic interaction. "
-----'-1t-t-l~,....----BMO
yl
<1>1
m
(a) (b)
• J = -ve for the singlet ground state, i.e. antiferromagnetism
he
• J = +ve for the triplet ground state, i.e. ferromagnetism
Fig. 8.29.1.1 (a) Formation of three centred MOs and their energy order (qualitatively) for the linear segment
M-X-M; (b) Energy separation (2J) between the ground singlet state and excited triplet state. lc
ea
(Note: In terms of group orbital formation or TASO, i.e. terminal atom symmetry orbitals, the two
eg orbitals will undergo the combination d Z2 ± d Z2 • These TASOs will undergo combination with the
ligand pz orbital to produce the 3 centered MOs.)
th
If I1E ) P (i. e. pairing energy), then the electronic configuration <f>y <f>~ will give the singlet ground
e/
state (i.e. antiferromagnetic interaction) This is the GKA rule.

It may be noted that participation of the d x 2 -y 2 orbital (another member of the eg set) with the
t.m
Pa-orbital (say Px) of the 'ligand will produce the similar MO energy level diagram.
B. Involvement of the t 2g orbital and ligand P7t orbital: We can illustrate for t2~(M) - p;'(L) - t2~(M)
180 0 superexchange. For the linear M-L-M segment, we can have three n-MOs (BMO, NBMO and
e
ABMO). These are illustrated in Fig. 8.29.1.2.

er
H
k
lic
x
C
GKA rule: 1800 superexchange

producing an antiferro-
magnetic interaction.
Bonding 1t-MO (~): dxy(M) + py(L) - dxy(M)

Nonbonding n-MO (~): dxy(M) + py(L) + dxy(M)
Antibonding n-MO (~): dxy(M) - py(L) - dxy(M).
Fig. 8.29.1.2 Formation of three centred 1t-MOs for the linear M-L-M segment.
Depending on the relative values of ~ (energy difference between <1>2 and <1>3 1t-MOs) and pairing
energy (P), for the d~ (M)-p; (L)-d~ (M) ,interaction, we can have the following electronic configurations.
• <l>r <l>i ~ (when dE) P), i.e. singlet gr~und state leading to an antiferromagnetic coupling (GKA
rule).
• <l>r <l>i <l>l (when P ) dE), i.e. triplet ground state leading to a ferromagnetic coupling.
ry
(c) Effect of temperature: The energy separation (~between the <1>2 and <1>3 MOs is not generally too
high. Consequently, at higher temperature (i.e kBT ~ ~), the population density at the excited triplet
ra
state will increase, i.e. antiferromagnetic coupling will destroy.
ib
8.29.2 Molecular Orbital Approach for'the 90 0 Superexchange Interaction
yl
Involvement of the eg ~rbitals and Po ,~rbitals of the bridging atom: This is illustrated
for d x' -l (M) - P(J (L) - d x' _y' (M) and d z' (M) - P(J (L) - d z' 90° superexchange interactions in Fig.
m
8.29.2.1.
he
In 90° superexchange, two metal d-orbitals and two ligand p-orbitals are involved. They will produce
two bonding (b <1>2) and two antibonding (<1>3' <1>4) MOs (cf. Fig. 8.29.2.2a).
lc
(Note: Fig. 8.29.2.1 indicates that the d x 2 -y 2 orbital of one metal centre participates in a-type
interaction with the ligand px-orbital and this dx2 _y2 orbital does not interact with the ligand py-orbital.
ea
Thus this segment produces one bonding MO and one antibonding MO. The three electrons are distributed
as: 2 in the BMO and 1 (unpaired) electron in the ABMO. For the perpendicular segment involving the
th
d x2 _ y 2 orbital of another metal and Py orbital of the ligand (where Px cannot participate), we can have
also one BMO and one ABMO. The three electrol1s are distributed between these two MOs, i.e. 2 in the
e/
BMO and 1 in the ABMO. Thus, there are two unpaired electrons in total (i.e. triplet state) in the two
t.m
ABMOs).
x x
e
er
x
H
k
lic
z
x
C
dZ 2
Bonding Combination: d Z2 (M) - pz (L) + Px (L) + d Z2 (M)

Bonding Combination: dX2_y2'(M) - Px (L) + Py (L) + d X2 _y2 (M)
Fig. 8.29.2.1 Pictorial represention for the 90 0 superexchange by using the Po orbitals of the bridging atom and eg
orbitals of the metal centres. .
3, ,
<1>~
/// ~E \
/// '" '" \ <1>;
/ ",'"
// 14 \
/ <1>3 1 <1>4 \ ==~14t::=:=l('" '" \ \
\
\\'
/
// \
Two metal \ , \\
==~,=1t:===::::;(
ry
\ d-orbitals '\ ' ,
Two metal
d-orbitals
\
\
\
\
""
\,
"'\'\
ra
\ \ \, '\
\ \
", , '\' \
\
\
\
\ \ , '\
ib
\
\
\
\ \\ '\
) ~& 1b
\ \
\, \ ,
yl
\ \ 4L 16 .,/
, \ ""~/ Two ligand
'
\ /// Two ligand
<1>2 , ~ // p-orbitals
,
m
\ // p-orbitals /
\
~n;=4it:L ====/ / \
, /
/
~ ~
he
<1>11 ~2 (~E) P)
GKA rule: 90° superexchange
producing a ferro- (b) Singlet state
(a) Triplet state
magnetic interaction. lc
ea
/\
Fig. 8.29.2.2 Approximate MO energy diagram for 90 0 superexchange (a) M - L- M = 90 0 (a case of accidental
orthogonality where the two magnetic orbitals are not mutually orthogonal but the ligand p-orbitals leads to the 90 0
th
/\
exchange), (b) M - L - M > 900 but < 1800 (cf Figs. 8.31.2.5a, b).
e/
From Fig. 8.29.2.2a, it is evident that there are two 'singly occupied molecular orbitals (SOMOs).
These are basically the antibonding MOs. It gives the triplet ground state, i.e. ferromagnetic coupling
t.m
which is the GKA rule.

/\
When the M - L- M bond angle increases (towards 180° along the x-axis), the a-type interaction
between the metal d x 2 -y 2 Qrbital and the ligand Pv- orbital decreases but the a-type interaction of the
e
ligand Px orbital with the two metal d x 2 -y 2 orbitals increases (cf Fig. 8.29.2.1). Similarly, with the
er
increase of bond angle along the z-axis, the a-type interaction between the metal d Z2 orbitals and the
H
ligand Px orbital decreases but the interaction of ligand Pz orbital with the two metal d Z2 orbitals
increases (cf Fig. 8.29.2.1). Consequently, degeneracy between the <PI and <P2 BMOs is lifted. Because
k
of the same ground, with the increase of bond angle the degenracy between the <P3 and <P4 ABMOs is
destroyed. Thus, for the higher bond angle, the MO energy diagram transforms into Fig. 8.29.2.2b. In
lic
Fig. 8.29.2.2b, the singlet ground state (i.e. antiferromagnetic coupling) prevails under the condition
~) P (pairing energy). For the condition, P) ~, the triplet state (i.e. ferromagnetic coupling) is the
C
ground state. It may be noted that for the 90° bond angle (cf Fig. 8.29.2.2a), the triplet state is the
/\
ground state. Thus, the nature of superexchange interaction depends on the M - L- M bond
angle. In fact, for the Cu-O-Cu bridging (J.!-hydroxido or J.!-alkoxido bridge) in the binuclear
complexes, it has been found that for the bond angle) 97.5°, the antiferromagnetic interaction
predominates while for the bond angle ( 97.5°, the ferromagnetic interaction prevails.
/\
Here it should be mentioned that at the limiting condition (i.e. M - L- M = 180°), one ligand
p-orbital becomes totally nonbonding (i.e. Pv. orbital for the metal d x 2 -y 2 orbitals, Px orbital for the
metal d z2 orbitals; cf. Fig. 8.29.2.1). In this situation, the MO energy diagram transforms into the
diagram as shown in Fig. 8.29.1.1.
The magnetic exchange interaction in " Cu/II0 " Cu/ II has been explained in terms of the MO
/' '0/ "
energy diagram in Sec. 8.31.2.
ry
8.30 ANTIFERROMAGNETISM IN MAGNETICALLY CONCENTRATED SYSTEMS:
ra
PATHWAYS OF ANTIFERROMAGNETIC INTERACTIONS
Ferromagnetism interaction enhances the paramagnetism while the antiferromagnetism leads to de-
ib
crease the paramagnetism. These aspects have been discussed in Sec 11.16.3. (Vol. 2).
yl
8.30.1 Types of Antiferromagnetic Interaction
m
Here we shall discuss the antiferromagnetic interaction in different complexes in detail. There are two
types of antiferromagnetism: intermolecular and intramolecular. Intramolecular interaction arises
he
when the interacting paramagnetic centres lie within the same molecule which may be binuclear or
polynuclear or dimeric or polymeric. The intermolecular interaction describes the interaction between!
among the different molecular species. lc
Measurement of magnetic susceptibility in solution or in a diamagnetic isomorphous host lattice (i.e.
ea
isomorphous dilution) may help us to distinguish between the intramolecular and intermolecular
interaction. In solution or isomorphous dilution, intermolecular interaction is prevented but intramo-
th
lecular interaction remains unchanged (cf. inter- and intramolecular H-bonding).

Examples of intermolecular antiferromagnetism: This type of interaction generally takes place
e/
over the entire crystalline lattice. The transition metal oxides and halides (e.g. KMF3, M = bivalent
transition metal ions) are the representative examples. In such cases, the magnetic susceptibility in
t.m
solution or in a diamagnetic isomorphous host lattice is higher than that found in their crystalline solid
state.
Examples of intramolecular antiferromagnetism: Some representative examples are given below:
e
(i) CU2(CH3C02)4-2H20: It is a dimer of copper(II) acetate monohydrate. It should show the magnetic
er
moment 1.73 B.M. per copper centre but it shows about 1.4 B.M. per copper centre at ordinary
temperature. This reduced magnetic moment arises due to the antiferromagnetic coupling
H
(8-bonding and/or superexchange).

(ii) Cr2(CH3C02)4-2H20: Cr(II) (t2~ ei) is expected to be paramagnetic but the dimer is diamagnetic
k
due to the antiferromagnetic interaction (quadruple bonding).

lic
(iii) K4[ClsRuIV_0-RuIVClsl: In the mononuclear complex, Ru lV (tr i.e. t 2i) is expected to bear
two unpaired electrons but the dinuclear species is diamagnetic due to an antiferromagnetic
C
exchange process.
(iv) [Re2Clsl2-: Its diamagnetic character can be explained by considering the antiferromagnetism
attained through the quadruple bonding (cf. Sec. 9.19, 12.8 of Vols. 2, 3).
8.30.2 Mechanism of Antiferromagnetic Interacti~n

The opposing spin alignment may be obtained either through the direct metal-metal interaction via
the overlap of suitable metal d-orbitals bearing the unpaired electrons or through the superexchange
process which involves the overlap of the d-metal orbitals bearing the unpaired electrons with the
orbitals of the bridging atom or group between the metal centres.
8.31 COOPERATIVE MAGNETIC INTERACTION IN COPPER(II) DINUCLEAR COMPLEXES

8.31.1 Antiferromagnetic Interaction in Carboxylato-Bridged Dinuclear Copper(lI)
Complexes: Dimeric Copper(lI) Accetate Monohydrate
Dinuclear tetrakis(J.l-carboxylato)-bridged copper(II) complexes like CU2(CH3C02)4· 2H20: The
structural and bonding features of this dimeric complex have been discussed in detail in Sec. 9.19 and
ry
Sec. 12.8.1 (Vols. 2 and 3).
The Cu-Cu distance in the dimeric form is 264 pm (cf. Cu-Cu distance in the metallic copper =
ra
256 pm). At room temperature, J.1obs is slightly less than the J.1spin-only value (1.73 B.M. per Cull-centre).
With the increase of temperature, J.1obs tends to reach the limiting value 1.73 B.M. To explain the
ib
observed subnormal value, two concepts, i.e. direct metal-metal bonding and superexchange interac-
yl
tion through the bridging acetate bridge have been suggested. However, there is a debate regarding the
actual path of this antiferromagnetic interaction.
m
a
(A) Metal-metal bonding: Each Cu(II) centre in the dimeric form has attained the distorted
octahedral structure where at the basal plane, oxygen atoms of the bridging acetate groups take the
he
positions (Fig. 8.31.1.1). The energy order of the d-orbitals is as follows:
d xz (1~), d yZ (1~) < dxy (1~) < d Z2 (1~~ < d X2 _ y2 (1)
OH 2
lc
ea
A ·'1 oX::I"
"I ---- ---- I···.
th
.... I Cu I ".
CH3-)<:': I I': -CH 3

.... o-----l----~ .....
e/
',.' I ....
0---- +----
'. I 1/' 3
: .... 0
t.m
CH3- , . I I I', C-CH

". I Cu I ....
'. I I .'
"1
0---- -----
6"
e
(b)
er
1
Triplet (8 8*1)
- - - - - : - - - - - E = _.!- J
H
\8-
I \ 5=1 2
I \
I \
I \
I \
k
I \
J =-ve
1-+----el: ~E >J----1-+---
lic
d-2-_y-2 2J, (cf. Fig. 8.31.1.4 and

x
Appendix VIII F)
" " d x2_ y2
\ ' 8=0
~E > P) E=+~J
C
\
"--++r--&-_''
(c)
"
8
(Assuming
(d)
2
Fig.8.31.1.1 (a) Dimeric structure ofCu(CH3C02h· H20; (b) Schematic representation of the overlap of the d 2 2 orbitals
x -y
leading to a O-bond; (c) Singlet state in terms of the o-MO-s of the dim~ric form of Cu(CH 3C0 2h·H20; (d) Energy of
the states in terms of J. Some authors denote the energy difference by J not by 2J.
(Note: Actually, in the formation of the MOs, besides the metal d x 2 -y 2 orbitals, the 1t-orbitals of the bridging acetate
contribute significantly. Participation of these bridging ligand 'orbitals is commonly described as the superexchange
pathway. There is a debate regarding the extents of direct exchange and superexchange*)
The 3d 2 2 orbitals bearing the unpaired electron on each Cu(ll) centre undergoes a lateral overlap
x -v
to form a weak delta bond (Fig. 8.31.1.1).
If the direct exchange pathway (i.e. through the formation of 8-MOs) is considered to bring about the
spin pairing, then from the simple MO-diagram (Fig. 8.31.1.1), it is possible to calculate the exchange
couping constant (1).
ry
1 1 1
Singlet (Bl B*o) and triplet (Bl B*l): Esinglet = -2 x -~ + P;
and Etriplet = --~ + -f1E = 0;
2 2 2
ra
Esinglet - Etriplet = 18£ - PI = 1211, (see Fig. 8.31.1.4)
ib
P-I1EI
1 = --2-' P = pairing energy;
yl
I
• when I1E ) P, singlet ground state, i.e. 1 is -ve
m
• when P ) 8E, triplet ground state, i.e. 1 is +ve.
he
1211 =::: 295 em-I, i.e. even at room temperature (kBT =::: 200 em-I), the excited state is also significantly
populated. It is evident that for the antiferromagnetism (i.e. singlet ground state), 1 becomes negative
lc
and for the ferromagnetism (i.e. triplet ground state), 1 becomes positive.
The electronic configuration in the 8-MOs is: 8~ 8* (singlet, S = 0, i.e. diamagnetic). Here it may be
ea
mentioned that the said B-bonding is relatively weak and it leads to only a partial spin pairing. In
fact, even at ordinary temperature, the equilibrium, singlet (8~ 8*°) ~ triplet (86 8*1) exists. In causes
th
only a partial spin pairing. This is why, the magnetic moment is only slightly decreased from 1.73 B.M.
(I-!spin) to 1.4 B.M. per copper centre. If some electron withdrawing groups are introduced in the
e/
acetate moiety, then positive charge on the Cu(II) centre increases. It causes an increased repulsion
between the Cu(ll) centres to weaken the 8-bonding interaction. This is why, with the increase of
t.m
electron withdrawing inductive effect of the acetate moiety (reflected with the decrease of pKa val-
ues), the magnetic moment (J.1obs) gradually increases.
e
Table 8.31.1.1 Magnetic moment of [Cu(RC0 2h·H 20h

er
J.lobs (H.M.) per Cu(II)

H
CH 3C0 2H 4.76 1.40

CICH 2C0 2H 2.60 1.42
k
C1 2CHC0 2H 1.25 1.65

lic
C1 3CC0 2H 0.65 1.77

F3CC0 2H 0.23 1.90
C
HC02H 3.75 1.65
Here it may be mentioned that the energy difference between the 8b and 8* MOs is not very high and
this energy separation (f1E) is comparable to the thermal energy (kBT). Thus the triplet state, i.e. 86 8*1
(S = 1, paramagnetic) is also populated to some extent at room temperature. Consequently, both the
diamagnetic singlet state and paramagnetic triplet state contribute to XM according to their population
densities governed by Boltzmann distribution law and multiplicities of the states.
(B) Superexchange interaction via the bridging carboxylate group: There are strong evidences to
support the fact that the antiferromagnetic coupling in [CU2II(RC02)4L2] (L = monodentate ligand like
H20, py, NCS-, etc.) is attained through the superexchange pathway involving the bridging carboxylate
group. The evidences are discussed below.
(i) Reduced fJ.eff in spite of large Cu-Cu distance in the formato complex: In the layer structure
of cupric formate tetrahydrate, Cu(HC02)2 ·4H20, the Cu-Cu distance in each layer is . . . 580 pm while
the Cu-Cu distance between the adjacent layers is 620 pm. Thus it is reasonable to assume that this
Cu-Cu long distance (cf. Cu-Cu distance in metallic crystal is 256 pm) does not allow the direct
ry
Cu-Cu interaction through 8-bonding. Besides this, the acetate group is more electron pushing than
ra
the formate group. Thus in the formate complex, there is an accumulation of more positive charge on
the Cu-centre. It also further disfavours the direct metal-metal bonding. To explain the lower magnetic
ib
moment in the formato complex compared to the J.!spin value (= 1.73 B.M.), the superexchange pathway
through the formate ion in the same layer is argued to operate.
yl
(ii) Magnitude of the exchange coupling constant (J), not correlated with the Cu-Cu separa-
m
tion: The 1-value gives the measure of energy separation between the singlet (ground state) and triplet
state (excited state). If 8-bonding is supposed to be the operative mechanism for the said antiferromagnetic
he
interaction, then the J value (magnitude) should decrease with the increase of the Cu-Cu distance
but the results do not support this prediction. Thus it is reasonable to argue that the antiferromagnetic
coupling is attained through the superexchange path not through the direct metal-metal bonding.
lc
The magnitude of exchange coupling constant (1) has been found to increase with the Cu-Cu
ea
separation.
[Cu2(CH3C02)4(OH2)2] [Cu2(CH3C02)4(NCS)2]2- [Cu2(HC0 2)4(NCS)2]2-
th
Cu-Cu (pm): 264 264 271

21 (em-I): -295 -305 -485
e/
(negative value of J indicates the antiferromagnetic exchange interaction, cf. Sec. 8.28.1).
t.m
Dimeric copper(ll) formates show the much the larger 1-211 values (.. . 500 em-I) than the correspond-
ing copper(ll) acetate dimers whose 1-211 values are about 300 cm- I but formic acid (pK(I ~ 3.75) is a
much stronger acid than acetic acid (pK(I ~ 4.75) and the Cu-Cu distance in the formato con1plex is
longer. In terms of the B-bonding concept (i.e. direct metal-metal bonding), in the formato complex, the
e
antiferromagnetic couping should be weaker compared to that in the acetato cOlnplex. But, experimen-
er
tally, the reverse is found true. Thus the most attractive question is: Why does the formato complex
show a higher 1-2JI value than the corresponding acetato complex?
H
The magnitude of the antiferromagnetic exchange has been found to increase in the following order:
k
Cu(lI) :-::-::~'"
lic
" CH-R, R=CH 3 <H<SiH 3

c/
Cu(lI) =..:..:..:
C
(iii) Independance of the exchange coupling constant (J) of L for [Cu2(CH3C02)4(L)2]: For
[Cu(CH 3C0 2)2(L)]2, the antiferromagnetic coupling constant does not depend on the nature of the
monodentate ligand L (e.g. H20, py, urea, NCS-, etc.). The electron density on the metal centre depends
on the nature of L to some extent. Thus 8-bonding (i.e. direct metal-metal interaction) should depend
on the nature of L to some extent. On dehydration of [Cu ll (CH 3C0 2)2(OH 2)12, the magnetic behaviour
(i.e. XM vs.n does not change. All these indicate that the direct metal-metal interaction does not play
an important role to determine their magetic behaviour.
(iv) Absence of Bb ---+ B* transition: If there is a 8-bonding in [Cu(CH 3C0 2 )2(OH:JJb there should
be a spectral transition, 8b ~ 8*. In fact, this spectral transition explains the colour of [Re2Cls]2- (blue)
and [M02 CLs]4- (red) (see Sec. 9.19, Vol. 2). But, the electronic spectrum of [Cu(CH 3C0 2)2(OH 2)]2
does not show any such metal-metal transition. The assigned spectral bands are:
d Z2 ~dx2_l (-11,000 em-I); d ty ~dx2_/ (17,000 em-I),
d tz ' dYZ~dx2_/ (14,400 em-I). Ligand ~ M (27,000 em-I, LMCTband)
ry
The band assignments can be rationalised in terms of the crystal field splitting of the d-orbitals in a
ra
square pyramidal geometry (el the dxy orbital is stabilised more than the d xv dyz orbitals; Sec. 8.25.1).
ib
yl
m
he
lc
ea
Fig. 8.31.1.2 Spectral transitions in a square pyramidal geometry of d 9 system
th
(v) Dependence of the exchange coupling constant (J) on the number of bridging carboxylate
groups: The i-value measuring the singlet-triplet energy gap significantly depends on the number of
e/
the bridging carboxylate groups. The value decreases in the sequence:

tetrakis(J.l-carboxylato) ~ bis(J.l-carboxylato) ~ mono(J.l-carboxylato)
t.m
With the decrease in the number of the bridging carboxylato group, the Cu-O-C bond angle
increases. The larger Cu-O-C bond angle weakens the overlap between the d x2 _ V2 (i.e. magnetic
orbital of copper(II» and the px-orbital of the bridging carboxylato group (ef Fig'. 8.31.1.3). This
e
observation supports the superexchange pathway for the antiferromagnetic interaction.

er
(C) Orbitals involved in the superexchange pathway: The d x2 _,i orbital of Cu(II) bearing an
H
unpaired.electron is the natural magnetic orbital (NMO) of copper(II). The NMO has the tails on the
bridging carboxylate group. The Cu-O-C-O-Cu bridge brings about the superexchange interaction.
k
The superexchange mechanism may arise through the overlapping of the d X2 _ y2 orbitals of the
lic
Cu-centres and n-MO (delocalised) of the bridging carboxylate group. The possible combination is:
C
d~2_,/ (Cu) + P~ (0) + P~ (C) + P.; (0) + d.~.2_y2 (Cu).

o
(assuming the Cu-eentres in the parallel xy-plane and the bridging R - C( skeleton in the
o
yz-plane; C uses the s, Py and P: orbitals for sp 2 hybridisation in. making the a-skeleton, i.e. Px orbital
is available for the n-MO formation).
It leads to 5 MOs and the singlet state is attained by placing the 6-electrons in the three lower MOs.
The higher vacant MOs are not far above from the HOMO. Thus the energy gap between the HOMO
and LUMO is not very high. The available thermal energy may excite the electron from the HOMO to
the LUMO and it leads to the triplet state. Thus, at room temperature the triplet state is also populated
to some extent. Because of this thermal equilibrium between the singlet and triplet state, the
antiferromagnetic coupling is incomplete.
ry
..... Px
ra
ib
yl
m
c
he
o a-skeleton
'~C-R lies in
lc 0'/ yz-plane
ea
Fig. 8.31.1.3 Schemetic representation of superexchange mechanism of interaction in the binuclear Cu(II)-acetato
th
complex using the 1t-orbitals of the bridging carboxylate moiety.

e/
(D) Dependenc~ of XM and J.Lobs on temperature for [Cu(CH3C0 2)2(OH2)]2: From the above
discussion, it is evident that for this dinuclear copper(ll) complex, both the concepts, i.e. antiferromagnetic
t.m
interaction in terms of 8-bonding involving the direct metal-metal interaction and superexchange through
the carboxylate bridging moiety can generate the singlet and triplet states.
In terms of Heisenberg-Dirac-Van Vleck (HDvV) model, the isotropic exchange Hamiltonian for
the exchange-coupled dinuclear complex is given by:
e
= -2JS, Sz, S, = Sz = S' (say) = ~, 2J = singlet-triplet energy gap.

er
H
2
H
For 5' = ~, the binuclear system may lead to the resultant 5 values as 0 and 1. Energy of a particula[
2
k
5-1evel is given by (see Appendix VIII F):

lic
3 1
Es = -J[S(S + 1) - 2S'(S' + I)J ' i.e. Es=o = +2,J and E s=' = -2,J
C
For the antiferromagnetic interaction, the level with 5 = 0 is taken as the ground state. It leads to:
~s,o =Es -Eo =-1[5(5+1)-25'(5' +1)J-215'(5' +1)=-1[5(5+1)]
i.e. E(5 = 0) - E(5 = 1) = 21
5 = 0 (ground state, singlet), 5 = 1 (excited state, triplet)
1 = -ve for antiferromagnetic interaction, 1 = +ve for ferromagnetic interaction.
The Zeeman perturbation does not split the ground state but splits the triplet state (5 = 1) as shown
in Fig. 8.31.1.4.
" ""
""
""" g~H
8=1
""" gPH
ry
" ,'----~-- E = _l - g~H
J
2
ra
ib
2J
yl
m
+~J -.-;....--------- - - - -- -- - - - - - - -
he
E=
2 8=0
Fig. 8.31.1.4 Zeeman perturbation on the singlet (5 = 0) and triplet (5 = 1) states for the exchange-coupled dinuclear
lc
Cu(II) complex.
ea
The susceptibility per gram atom of copper is given by van-Vleck equation simplified by Bleaney
and Bowers.
th
XCu -
_ N AP2 g2 [ 1
l+-exp - - -
(21 J]-1 +NAu,
(BleaneY-Bowers equation, J
e/
3k BT 3 kBT see Appendix VIII-F

t.m
At very low temperature only the diamagnetic singlet state is thermally populated but at the
relatively higher temperature both the singlet and triplet states are populated to contribute to the
susceptibility.
1600 ,...--,.....--~-,.....----,r---
e
_ _r------,
2.0,...------------------,
er
1200
~
H
"0
E
ME 800 i 1.0
k
CDO
0.,-. ~
lic
~ 400
C
100 200 300 400

50 100 150 200 250 300
Temperature (K) Temperature (K)
(a) (b)
Fig. 8.31.1.5 Temperature dependence of molar susceptiblity and effective magnetic moment for diaquatetrakis-J!-
acetatodicopper(II).
Note: If TIP and contribution from the monomeric forms as impurity are ignored, then in such binuclear
systems (s\ = =±),
S2 Ilctl is given by:
~eff = gp[ 1+ ~exp( - k2:T )

In absence of cooperative interaction, i.e. 1
r I
2
= 0, we have:
I
~eff =gp(1+~r2 =gpj{ =J3P=~S(S+l)P=l.73P,
ry
forg=2 andS=±; and
ra
= NA~2g2 i xl = N
2
(1+!)-1 = N A p A p2 g 2
XCu 3k BT 3 3k BT 4 4k BT
ib
For diaquatetrakis(fJ.-acetato)dicopper(II), NAa has been found 60 x 10-6 cm 3 mol- 1 per copper
yl
centre. Thus, NAa (i.e. TIP) is quite negligible. For this complex, the plot XCu vs. T indicates the maximum
value of XCu at about 260 K while XCu becomes negligible below 100 K (ef Fig. 8.31.1.5). But below
m
50 K, further cooling leads to a slight increase in XCu value. This effect arises because of the presence
of a small amount of noncoupled monomeric species. Thus the above equation is modified as follows:
he
XCu = N A p2 g 2 [I+!exp(-~J]-l (I-x)+ N Ap2 g 2 x+NAu
3k BT 3 kBT lc 4k B T
ea
where x denotes the mole fraction of noncoupled species. The monomeric impurity follows the Curie
law. Neglecting NAa, we can write the Bleany-Bowers equation as follows:
N A~2 g2 [ )]-1 (l-x)+ N Ag2~2 x

th
1 (21
XCu ~ I+-exp - - - .
3k B T 3 kBT 4k B T
e/
Analysis of the experimental findings indicates:

21 = -292 cm- 1, g = 2.16, x ~ 0.02, i.e. 2%
t.m
8.31.2 Cooperative Magnetism in the Di-Hydroxidobridged Dinuclear Copper(lI)

Complexes in Terms of Structural Parameters
e
• Nature of cooperative magnetism depending on the LCu-O-Cu angle: Cooperative magnetisnl

er
in the di-hydroxidobridged dinuclear copper(II) complexes has been found to depend on the Cu-Cu
distance and Cu-O-Cu angle (a). The planar di-hydroxido-bridged dimer possesses the bidentate
H
nitrogen containing ligands.

k
lic
C
Table 8.31.2.1 Variation of magnetic properties with Cu-Cu distance and Cu-O-Cu bond angle in
di-Jl-hydroxidoCu(lI) dimers
Complex Cu-Cu LCu-O-Cu 2] (em-I)

(pm) (degrees)
[Cu(bpy)(OH)h(N0 3h 284.7 95.5 +172

[Cu(bpy)(OH)h(S04) 289.3 97 +49
[Cu(eaep)(OH)h(CI04h 291.7 -99 -130
(Collfd.)
Complex Cu-Cu LCu-O-Cu

(pm) (degrees)
[Cu(2-miz)(OH)h(CI04 h·2H 20 99.5 -175

[Cu(tmen)(OH)]2(CI04 h 293.5 100.5 -200
[Cu(teen)(OH)h(CI04 h 297.8 103 -410
ry
[Cu(tmen)(OH)] Br2 300.0 104.1 -509
ra
bpy = 2, 2'-bipyridine; eaep = 2-(2-ethylaminoethyl)pyridine; tmen = N, N, N', N'= tetra-methylethylenediamine; teen
= N, N, N', N'-tetraethylethylenediamine; 2-miz = 2-methylimidazole
ib
From Table 8.31.2.1, it is evident that with the increase of the LCu-O-Cu angle and Cu-Cu
distance, 1 value changes from +ve to -ve i. e. ferromagnetic interaction to antiferromagnetic interaction.
yl
The change-over from ferromagnetic exchange to antiferromagnetic exchange occurs at
LCu-O-Cu ~ 97.5°. Plot of 21 value (- sign for antiferromagnetic exchange, +value for ferro-
m
magnetic exchange) versus LCu-O-Cu angle is shown in Fig. 8.31.2.1. The results can be explained
he
by considering in two ways: projecting the dx2 _ ,,2 or d.1;y orbitals towards the bridging O-atoms of the
CU202 ring. .
200 lc
ea
100
0
th
i
-100
e/
-200
t.m
-300
'I
E
~ -400
J
C\J
-500
e
-600
er
97.5
95 97 99 101 103 105
H
LCu-O-Cu (in degree)

k
Fig. 8.31.2.1 Variation of J with the LCu-O-Cu angle in the CU202 ring system.
lic
(A) Interpretation in terms of 90° vs. 180° superexchange by considering the d x 2 _ y2 orbitals
projecting towards the bridging O-atoms of the CU202 ring: The observation can be explained in
C
terms of 90° vs. 180° superexchange of GKA rule (Secs. 8.28, 8.29.2). The unpaired electron of Cu(II)
resides in the d x2 _ v2 orbital and the lobes of this orbital are projected towards the bridging atoms.
Orientations of the orbitals for the overlap interactions are shown in Fig. 8.31.2.2. For the 90°
superexchange interaction (i.e. 90° bond angle), the bridging oxygen uses its pure p-orbitals (i.e. Px and
P.J. When the bond angle opens towards 180°, one p-orbital of bridging oxygen tends to fail to interact
with the metal d x2 _./ orbitals while the interaction with the other p-orbital gradually increases. In the
o
limiting situation (i.e. 180° bond angle), one p-orbital becomes nonbonding while the other p-orbital
can make a very good a-type overlap with the metal d-orbitals (see Figs. 8.29.2.1, 2). In terms of the
GKA rule and simple molecular orbital treatment (cf Secs. 8.28, 8.29.1, 2), it leads to the ferromagnetic
exchange in 90° superexchange (case of accidental orthogonality causing a ferromagnetic exchange)
and antiferromagnetic exchange in 180° superexchange. Thus, it is quite reasonable to expect that
with the increase of LCu-O-Cu bond angle a ferromagnetic exchange will switch over to an
antiferromagnetic exchange.
The 90° bridge angle is attained when the bridging O-site uses its pure p-orbitals for bridging. For
ry
the bridge angle) 90°, the bridging O-site uses the s-p hybrid orbitals for the bridging.
[Note: It is evident that for the LCu-O-eu angle = 90°, the superexchange leads to a ferromagnetism
ra
(cf Figs. 8.28.4.2b, c, 8.29.2.1 and 8.31.2.2). In such cases, the two magnetic orbitals of the metal
centres are said to be accidentally orthogonal (see Sec. 8.32.1 for strict orthogonality). The word
ib
accidentally has.
been used to signify that the two concerned magnetic orbitals (i.e. d x 2_ },2) are not
yl
mutually orthogonal. In fact, they are of the same symmetries. Here it may be mentioned that the
m
d X2 _y2 and dxy orbitals are strictly orthogonal (cf Fig. 8.31.2.3 and 8.32.1.4).]
he
(B) CuzOz ring system vs. CrzOz ring system by considering the d x 2 -y 2 orbitals projecting
towards the bridging O-atoms: Here it is interesting to compare the magnetic exchange interaction in
the CrzOz ring (CrIll: t~g) and CuzOz ring (CUll: square planar arrangement around the copper centre).
lc
In the Cr(lll) system, the unpaired electron resides in the t 2g level and these magnetic orbitals are not
ea
directed towards the filled p-orbitals of the bridging O-atoms. On the other hand, in the Cu(II)-system,
the unpaired electron resides in the d x2 _ V2 orbital which is directly projected towards the filled
th
p-orbitals of the bridging O-atoms. Thus, the superexchange interaction in the CrzO z ring is rela-
tively weaker than that in the CuzOz system.
e/
y~ x
,, Jf
t.m
y , /
/
/0
/
~...
... Px
...
...
Py
~
e
\
0
"-
... Cu 90 Cu
er
L
0 ~900
H
//~ x 0
;
;L
k
Cu / { d xy (denoted by
lic
" dotted line)

) Cu
C
d x2 _ y 2
\
...
\
0 ...
"-
,L
"-
\
\
Py
(a)
+y
I
I
ry
ra
ib
yl
Cu
m
he
lc
ea
L CU"-O-CU" = 90 0
(b)
th
y
e/
+I
I
t.m
e
er
H
k
lic
L CU"-O-CU" = 180 0
(c)
C
Fig. 8.31.2.2 Considering the d x2 _ \'2 orbitals projecting towards the bridging O-atoms. (a) 90 0 superexchange in CU 20 2
ring (ef W. Geertsma and D. Khomskii, Phys. Rev. B. 54,3011,1996). (b) 90 0 superexchange in LCu-O-Cu segment
(el Fig. 8.29.2.1). (c) 180 0 superexchange in LCu-O-Cu segment (ef Fig. 8.29.1.1).
Note 1: Magnetic exchange interaction in the er(III) systems can be rationalised in terms of the
GKA rules. The 90° superexchange, d:y d;/~ i;)d~y (cf Fig. 8.28.4.2a) involving the t 2g orbital (i.e.
d.n) leads to a ferromagnetic exchange. But the 180 superexchanges, t~~ .1 p2 .1 t~l? (el Fig. 8.28.4.1c)
0
. 1 2 1 '(0") (0")'
and t 2x i;) P i;) t 2Ii(cf Fig. 8.28.3.5) lead to an antiferromagnetic interaction.
Note 2: The antiferromagnetic interaction through the direct d.~y-d.~y (CrIll) overlap (ef Fig. 8.32.1.lc)
is not effecient because the 3d orbitals are radially too contracted to make a good overlap. This aspect
has been discussed and compared for the d-orbitals of the heavier congeners (Sec. 8.32.1).
(C) l\lolecular orbital treatment for the CU202 ring (D 2h symmetry) by considering the dxy
orbitals projecting towards the bridging O-atoms: By considering the D 2h symmetry of the CU202
ring, some authors (Ref. DJ. Hodgson, Prog. Inorg. Chern., 19, 173, 1975) have explained the mag-
ry
netic behaviour (i. e. nature of J as a function of bridging bond angle) of the dinuclear complexes of
Cu(II) with the double oxido-bridges. In terms of D 2h symmetry, x-axis is lying along the Cu-Cu
ra
direction and y-axis is along the 0-0 direction (Fig. 8.31.2.3).
ib
yl
y
m
t
o
he
90°
CU~ Cu~x ---+

0
90 lc x
ea
o
th
e/
Fig. 8.31.2.3 Considering the drY orbitals projecting towards the bridging O-atoms in the D2h symmetry of CU202 ring,
t.m
orbital positions and reference a·xes.
Each Cu(lI)-centre bears an unpaired electron (s =~). Let us consider the available orbitals in the
e
xy-plane.
er
(i) Each Cu(II) centre will provide 2 orbitals, i.e. dxy and d.r 2 _ / •
(ii) Each O-centre will provide 2-orbitals, i.e. Px and p y.

H
Thus there will be 8 orbitals, i.e. d.,y, d.r 2_y2 , d.,y, d.r 2_y2 , P.\"' P.r. Py and Py for LCAO to produce 8
k
MOs. Out of these 8 MOs, there are 4 bonding MOs (i.e. Qg' bIg, b 211 and b 3//) and 4 antibonding MOs
lic
(i.e. (l.~:,b;1I and b 3;'). The orbital overlaps are shown in Fig. 8.31.2.4. and molecular orbital diagram
bIg,
is shown in Fig. 8.31.2.5a, b.

C
For LCu-O-Cu = a = 90°, the bIg and b 211 MOs are of identical energy; similarly, {lg and b 3u are
degenerate. With the increase of the LCu-O-Cu angle (i.e. a) 90°), dry(Cu)-Px(O)-dx.JCu) overlap
in bIg increases while the d.n·(Cu)-p/O) - dx./Cu) overlap in b 211 decreases. Thus with the increase
of bond angle, degeneracy of the big and b 2u orbitals is not maintained i.e. bIg becomes of lower
energy while b 2// becomes of higher energy. Similarly. with the increase of LCu-O-Cu bond angle
(i.e. a ) 90°) the degeneracy of the (lg MO i.e. d.r 2_\,2 (Cu) - P." (0) - d x2 _\,2 (Cu) and the b3li MO,
i.e. d.\_, _\: (ell) - P., (0) - d x2 _."2 (Cu) is destroyed and the G g MO becomes of lower energy compared
to the h.,,, MO.
For the antibonding MOs, with the increase of the bond angle (a) i.e. for a) 90, between a; and b3:
the degeneracy is lost and b3: becomes of lower energy compared to a;.
Similarly, for a ) 90 0 , b2;!;
becomes of lower energy than bl,~.
ry
Px
ra
ib
yl
m
he
(a g ) (b 3u )
Px
A
Cu a lc
Cu
""0/
ea
Px
th
e/
t.m
Px
e
er
Fig. 8.31.2.4 Considering the d\\" orbitals projecting towards the bridging O-atoms, schematic representation of orbital
H
overlaps in the CU202 ring system (D 2" symmetry) to produce the bonding MOs. Note: Similar orbital overlaps also
occur in the Cr202 ring system.
k
There are 14 electrons (dry and d. r2 _.r 2 orbitals of each Cull-centre contribute 3 electrons~ P.~ and p)
lic
orbitals of each 0 - will contribute 4 electrons~ i.e. total electron count = 2 x 3 + 2 x 4 = 14). These 14
2
C
electrons are to be accomlTIodated in the 8 MOs. The 4 BMOs will accommodate the 8 electrons and
the remaining 6 electrons are to be placed in the 4 ABMOs.
Case I: For LCu - 0 - Cu = 90°, the energy order of the ABMOs is:
Thus the 6 antibonding electrons are distributed as follows:

(0,;')2 (b);')2 (b I ,~) I (b 2;') I .
=
It leads to triplet ground state (i. e. S 1) i. e. ferromagnetic coupling.
/
,'+- +-\
b1g b2u \
I-tt- ---tt-\ \
I \
III
I II. • \ \
/ I ag b3u \ \
I I \ \
I I \ \
ry
I I \ \
dxy d
xy_ I I / \ \
___ I \ \
\ I \ \
ra
\ I \ \
\ I \ \
d X2 _ y
2
d x2 _
y
2 /\ \\
_ _ _ _I \ \\
ib
\ \ \\
metal a-orbitals
\\ \\ \\\\{PX
---
Px
\ \ 11---
yl
"\ "\ I /,'
I Py Py
" " / " ligand a-orbitals
m
\ \ I I
\ \ I I
\ \ I I
\\\\'*r",,'
\ \ I 1
he
\ I
\* *,'
" b 1g b2u ,'
lc
ea
ag b3u
Metal ion orbitals Molecular orbitals Oxygen orbitals
th
Fig. 8.31.2.5 (a) Molecular-orbital diagram for a-orbitals in the CU.202 ring system (assuming D 2h symmetry, d rr
orbitals projecting towards the bridging O-atoms) for LCu-O-Cu angle = 90 0 (Case of accidental orthogonality
e/
leading to ferromagnetism) (ef Fig. 8.29.2.2a).

t.m
e
er
H
k
lic
C
Metal ion orbitals Oxygen orbitals
Fig. 8.31.2.5 (b) Molecular-orbital diagram for a-orbitals in the CU202 ring system (assuming D2h symmetry, dry orbitals
projecting towards the bridging O-atoms) LCu- O-Cu angle) 90 0 (case of antiferromagnetism) «(f Fig. 8.29.2.2b).
Case II: For LCu-O-Cu ) 90°, the energy order of the ABMOs is modified as follows:
b3: ( a; (
b2: ( bl;
The 6 antibonding electrons are distributed as follows:
(b 3:)2 (a;)2 (b 2:)2 (b l;) whenf1E) P
where ~ = energy separation between b2: and bl; and P = pairing energy.
ry
= 0) i. e. antiferromagnetic coupling.
It leads to the singlet ground state (S
ra
But under the condition, P ) dE, the 6 antibonding electrons are distributed as follows:
(b 3:)2 (a;)2 (b 2:) I (b l ;) I
ib
It leads to the triplet ground (i. e. antiferromagnetic coupling).
yl
The energy separation (~) between the ABMOs b2: and bl; depends on the LCu-O-Cu bond
angle. With the increase of the bond angle from 90°, the energy separation (dE) increases. From the
m
experimental observation, it has been found that for LCu-O-Cu ) 97.5°, the condition dE ) P is
maintained to induce the antiferromagnetic coupling.
he
The important conclusions are given below.
(i) LCu-O-Cu::::: 90°, triplet state is the ground state i.e. ferromagnetic exchange (1) 0)
lc
(ii) LCu-O-Cu ) 97.5°, the singlet state is the ground state i.e. antiferromagnetic exchange
ea
(1 ( 0)
(iii) The LCu-O-Cu bound angle becomes close to 90° when the magnitude of s-character in the
th
bridging orbitals is less. It leads to a ferromagnetic exchange. When the magnitude of s-character
in the bridging orbitals is large, the bond angle opens up to induce the antiferromagnetic exchange.
e/
Here it is worth mentioning that the simple molecular orbital treatment (cf Figs. 8.29.2.1-2) also
t.m
leads to the same conclusions.

Note: The hydroxido-bridged Cr(III)-dimers also show the similar properties.
e
er
H
(D) CU202 ring system vs. Cr202 ring system in terms of the D 2h symmetry: For Cu(II), the
k
d x2 _y2 orbital bears the unpaired electron but for Cr(III), the t2g orbitals bear the unpaired electrons.
lic
The exchange interaction in the CU202 ring system is greater than that in the Cr202 ring
system. In fact, for a particular LM-O-M angle, the magnitude of i-value is larger for the CU202
C
system.
The MOs for the Cr202 ring fragment (considering the D 2h symmetry) can be constructed in the
same way «(1 Figs. 8.31.2.4, 5). Here it is noteworthy that in the Cr202 system, the exchange interaction
is relatively weaker. For the Cr~1I02 ring in the xy-plane, there will be 10 electrons (d~\, orbital of each
Crill contributes one electron; p} and p} orbitals of each 0 2- will contribute 4 electrons i.e. total electron
count = 2 x 1 + 4 x 2 = 10) to be distributed among the available MOs. In the Cr202 ring system,
electron distributions among the MOs obtained from the AOs in the xy-plane are as follows:
a = 90°: a; b~ll( br
g b~u( a,; I b3: 1
a > 90°: a,~ ( b~ll( bf~( bill( b;~, ~ (energy difference between a,; and b3~) ) P.
8.31.3 Antiferromagnetic Interaction in Other Dinuclear Copper(lI) Complexes

• Dihalido(pyridine- N-oxide)copper(II), dihalido( q uinoline- N-oxide)copper(II): The
antiferromagnetic interaction in their dimeric forms is attained through the superexchange pathway
involving the p-orbital of the bridging oxygen. It may be noted that in such compounds the Cu-Cu
distance is longer than that in [Cu2(CH3C02)4(OH2)2]'
ry
ra
ib
yl
m
he
lc
ea
(X = CI, ~ = 0.77 8.M. (X = CI, ~ = 0.6 8.M.
(X = 8r, ~ = 0.85 8.M.) (X = 8r, ~ = 0.4 8.M.)
th
Fig. 8.31.3.1 Structures of some dimeric Cu(II) complexes having the CU202 ring.
e/
t.m
e
er
H
k
V
lic
8identate bridging ligand

C
Fig. 8.31.3.2 Structure of dimeric form of bis(diazoaminobenzenato)copper(II)
• End to end azido bridged dinuclear copper(II) complexes: These are diamagnetic through the
antiferromagnetic interaction attained in the superexchange pathway mediated by the n-MO of the
symmetrical bridging ligand. Here, the triplet state is about 1000 cm- I above the ground state. Thus, the
excited triplet state remains thermally unpopulated.
L"" /N=N+ N"" /L

Cu Cu
L/ "N ===N+=== N/ "" L

• Bis(diazoaminobenzenato)copper(II): The ligand diazoaminobenzene, i.e. Ph-NH-N=N-

Ph acts as a bridging bidentate ligand in the dimer of the complex. The structure of the complex is very
much similar to that of dimeric copper(II) acetate.
The 8-bonding between the d x2 _ v2 orbitals of the two Cu(II) centres leads to a complete quenching
of the spin. Here it may be pointed out that as in the carboxylato-bridged complex, here the superexchange
pathway through the 1t-MO of the bridging ligand may also occur. In fact, the dimer is completely
ry
dimagnetic «(f. in the corresponding Cu(II) acetate dimer, only a partial quenching of the spins occur).
Thus in this dinuclear complex, the triplet state is far above the ground state.
ra
• Dimeric Schiff base complexes of Cu(II): They show a subnormal magnetic moment (i.e. IlctT
ib
( Ils pin). It is believed that the unpaired electron in the d x2 _ v2 orbitals of Cu(II) centres undergo the
superexchange interaction with the p-orbitals of the bridging oxygen. The antiferromagnetic interaction
yl
in the superexchange pathway between the Cu(II) centres can also be explained in terms of the
m
extended molecular orbital formation (cf Sec. 8.31.2).
he
lc
ea
(A representative example of a tridentate Schiff base)
th
Fig. 8.31.3.3 Structural representation of a representative dimeric Schiff base complex of eu(II).
e/
8.32 ANTIFERROMAGNETIC COUPLING IN OTHER COMPLEXES

t.m
8.32.1 Magnetic properties of the Dimers of Oxidovanadium(IV) and

Oxidomolybdenum(V) Complexes
Electronic configuration in the oxidovanadium(IV) and oxidomolybdenum(V) complexes:
e
Oxidovanadium(IV) and oxidomolybdenum(V) are the d l systems and in their five coordinate square
er
pyramidal complexes, the unpaired electron resides in the dxyorbital ((f. Sec. 7.14.1 and Fig. 7.14.1.3).
The energy order of the d-orbitals is:
H
d xy (i) < d x :.' d y:. < d./__ y2 < dz. 2

k
(A) Structural unit for cooperative magnetism: In some dimeric and polymeric forms, there is an
lic
octahedral coordination having the V= 0 axis along the z-axis. In such cases, the electronic configuration
is t2,~e,~). The coordination behavour of oxidomolybdenum(V) is very similar to that of oxidovanadium(IV).
C
The dinuclear oxido-complexes of Mo(V) (d l ) may have the following types of structures.
o o o o 0
11/ 11/ 11/ 1/ -Mo

11/°", 11/ Mo-
-Mo-O-Mo- -Mo-O-Mo-
/1 /1 /1 /11o / I "'0/ I
M0 2 0 4 core
~-----..y------
V
cis- and transforms of the singly bridged dimers Doubly bridged dimer
In all the monomeric and dimeric forms, the trans-bond to Mo= 0 is relatively weaker (in some
cases the corresponding trans-position may remain vacant). Thus, the energy order of the d-orbitals is
very much similar to that of square pyramidal geometry (cf Fig. 7.14.1.3). Consequently, the unpaired
electron resides in the lowest energy orbital dxy i. e. d)" even in the distorted octahedral geometry.
(B) Magnetic behaviour of the single oxido-bridged and double oxido-bridged
oxidomolybenum(V) complexes: For the eis- and trans-forms of the single oxido-bridged (O)Mo-
ry
O-Mo(O) segment which is almost linear, the antiferromagnetic interaction can be attained in the
ra
0
following a-type 180 superexchange path.
• 180 superexchange (a-type):
0
ib
(Mo)d~y ~ P.; (0 2- )~d.~y (Mo) (ef Figs. 8.28.4.1c, 8.32.1.1b)
yl
Here it may be mentioned that the following 180 0 superexchange (1t-type) can also bring about the
m
antiferromagnetic interaction.
0
• 180 superexchange (1t-type):
he
(Mo)d~y~p~(02-)~d~y(Mo) (cf. Figs. 8.28.3.5, 8.32.1.1a)
lc
It may be noted that the a-type superexchange interaction is more efficient than the 1t-type
superexchange interaction. Bending of the linkage will disfavour the above mentioned superexchange
ea
paths.
The antiferromagnetic interaction leading to the diamagnetism in the single oxido-bridged xanthato
th
complex M0203(S2CEt)4 is attained through the both dn-Pn bonding i.e. 1t-type 180 superexchange
0
and dcr-pcr bonding i.e. a-type 180 superexchange ((1 Fig. 8.32.1.1 a, b) pathways.
0
e/
t.m
e
er
In the above xanthato complex, the antiferromagnetic couplings are so efficient that the complex is
diamagnetic.
H
Antiferromagnetic
+y
~~ I
k
I
lic
C
IT-type 1800
superexchange:
x
(a)
~p,
+y
I
:~
a-type 180 0
Cj~
ry
superexchange:
----G~O
ra
ib
----.........----
yl
Antiferromagnetic
(b)
m
/7\
he
y ~'r: d
xy
x
lc
ea
th
e/
/,/ ~ all- ""'"

t.m
/
/ '"
e
(c)
er
Fig. 8.32.1.1 (a) Antiferromagnetic coupling through the 1t-type 180 0 superexchange in the single oxido-bridged M0 20 3
- core, (b) Antiferromagnetic coupling through the a-type 180 0 superexchange in single oxido-bridged M0 20 3 core,
H
(c) Direct metal-metal interaction leading to an antiferromagnetic interaction in the double oxido-bridged M0 20 4 core.
For the double oxido-bridged species, the d1yorbital bearing the unpaired electron is not suitable to
k
produce any efficient superexchange path by involving the filled p-orbital of oxygen. But bending of
lic
the Mo-O-Mo segments will bring the Mo-centres at a closer distance. This will facilitate the direct
metal-metal interaction through the a-type overlap of the dx.v orbitals (Fig. 8.32.1.1 c). Here it is worth
C
mentioning that the 02M0202 ring system may be treated in terms of MOT as in the case of Cr202 ring
(Sec. 8.31.2) to explain the antiferromagnetism.
(C) Magnetic properties of the Schiff base complexes of VO(IV): N-(hydroxyphenyl)-
salicylideneiminatooxidovanadium(IV) shows the subnormal magnetic moments. They remain as dimers,
e.g. [VO(salicylaldehyde-o-aminophenol)]2' The closely related compounds also exist as the dimers,
e.g. [VO(salicylaldehyde-ethanolamine)]2' etc.
In the dimeric forms, the oxygen atom (phenolic oxygen in 1, and alcoholic oxygen in 2, Fig.
8.32.1.2) of the tridentate Schiff base ligand acts as the bridging atom. The unpaired electron resides
in the dxy orbital i. e. d.\~ .. The vacant d.,..:. _./ orbital is projected towards the bridging atom. The super-
~o-v
II ____
R--~C=! L
ry
/ '" /' 2
H CH 2
ra
(1 ) (2)
ib
yl
m
he
lc
ea
(av) d~y III

th
IT • d:y(va)
(3) (4) (cf. Fig. 8.32.1.1c)

e/
Fig. 8.32.1.2 Structures of the momomeric and dimeric forms of Schiff-base (0, N, 0 tridentate character) conlplexes
t.m
of oxidovanadium(lV).
Antiferromagnetic interaction in the dimeric oxido-bridged complexes of

e
oxidovanadium(IV) and oxidomolybdenum(V)

er
a a a
I I
H
(i) M-a-M or
II
M-a-M d.~y - P.; (0) - d.~.y ( (J - type 180 0 superexchange)
II
k
d.~y - p.~ (0) - d.~.\. (1t - type 180 0 superexchange)

a
lic
C
l dl.\y (a -type d"Irect InteractIon)

.
(ii) d xy -
M = V(IV), Mo(V)
exchange process involving the filled p-orbitals of oxygen is not possible because the d x 2 -\' 2 orbital
is vacant. It may be mentioned that in the corresponding Cu(II) complex (ef Fig. 8.31.3.3), the unpaired
electron resides in the d.\,2 _."2 orbital and the antiferromagnetic interaction may be attained through the
superexchange process (el Sec. 8.31.2) depending on the Leu-O-Cu bond angle. The present
MAGNETOCHEM'STRV: MAGNETIC PROPERTIES OF METAL COMPLEXES 1249
system involving VO(IV) or MoO(V) forming the ring may treated in terms of MOT as in the case of
Cr202 ring (cf Sec. 8.31.2) to explain the antiferromagnetism.
In the dimeric form, the two dx.~. orbitals of the oxidovanadium(IV) centres are in the right position
for a O'-type overlap i.e. d~y ~ d~y interaction (Fig. 8.32.1.1 c). It will lead to spin pairing. It leads
to an antiferromagnetic interaction.
ry
(D) Efficiency of the direct d~y - d~y a-overlap: Now let us compare the efficiency of spin pairing
through the d;y- dly(O'-overlap) in the VO(IV)(3d l ) and MoO(V) (4d') dimeric complexes (cf Fig.
ra
8.32.1.3).
ib
yl
m
he
lc
ea
th
e/
t.m
, \ a*- ABMO
,, ,
, \ a*- ABMO
\ ,,, \
\
,,
\ \
, \ \
,, , ,,,
\ \
\ \
\ \
e
\ \
~: ~E ~ ksT \):----t- 1
~,
,\' ~E)ksT
\~
er
\
\
\\ ~E > P ,,
,, \
\ I
I
\ I
, \ ~E) P
H
,,
\ \ I
\
\ I
\
\ I
\~' \ I
k
\~'
a-BMO
~
lic
a-BMO
C
Fig. 8.32.1.3 Comparison of the antiferromagnetic coupling in the dimeric complexes of VO(lV) of MoO(V) through
the direct d{.y-
. .
d},.cr-type overlap (E Sine- · 1e t = 1M' - pi = 1211, cf.
.. 01 e t -- E t np . Fig. 8.31.1.1).
The larger 4d-orbitals can make a better overlap than the relatively smaller 3d orbitals. It makes
the energy separation (~E) between the o-BMO and o*-ABMO much larger for the dimeric Mo(V)
complexes compared to that for the corresponding V(IV) complexes. Because of the same ground, in
the dimeric complexes of Cr(III) having the Cr202 ring, the direct t 2g - t 2g interaction is insignificant.
In fact, for the V(IV) complexes, there is a thermal equilibrium (at room temperature) between the
singlet state i. e. (0')2 (0"'')0 and triplet state i. e. (0) 1 (O':~')'. The energy separation between the singlet
(5 = 0, ground state) and triplet (i.e. 5 = 1 excited state) states is measured by the 1211 values, i.e.
Esinglet -- Etriplet = 1L1£' - PI = 1211 (cf Sec. 8.31.1.1) and ~E(Mov) ) L1£'(V IV )
The Mo(V) aqua ion M0 20]+ (aq) (yellow) (4) is diamagnetic and the strong d~y(Mo) - d~y(Mo)
interaction leads to a Mo--Mo single bond. The structure of the oxalato complex (5) derived from the
aqua ion, M0 201+ (aq) is shown below.
ry
ra
ib
(4)
yl
L~~~L
m
he
f}u~arJ~
L
l
Q
---v-
)
L lc
ea
~ ~
Cu => Cu(lI) V=> VQ(IV) Cu => Cu(II), V => VQ(IV)
th
• Superexchange • Direct V-V • CU(II)dx~_y2..l dxyV(IV)

via the bridged interaction via the i. e. zero overlap integral
e/
O-atom* d-rr - drr a-overlap leading to a ferromagnetic

(antiferromagnetic when a > 97° (antiferromagnetic) exchange (case of strict
t.m
orthogonality*).
• Singlet (5 = 0) ground • Singlet (5 = 0) • Triplet (5 = 1) ground
state and triplet (5 = I) ground state and state and singlet
excited state** for triplet (5 = 1) (5 = 0)
e
LCu - 0 - Cu > 97° excited state. excited state.

er
8=1 8=1
J) :=0 I2JI
H
12 JI 12 JI
J<0 J <0
a> 97°
k
lic
8=0 8=0 8=1
Fig. 8.32.1.4 Considering the d x2 _,) orbitals projecting to the bridging O-atoms in the M 20 2 ring system (see Fig.
C
8.31.2.2), different types of interactio·n in the different oxido-bridged dimers consisting of the Cu(II) and VO(lV) centres.
(E) Cooperative magnetism in the heterometallic dimers: We have already mentioned that in the
case of the oxido-bridged dimers of Cu(II), the unpaired electron in d 2 2 can participate in the
x -\'
superexchange process through the involvement of the filled p-orbitals of the bridging O-atom (Sec.
8.31.2). In the case of heterometallic dimer consisting of the magnetic centres Cu(II) (unpaired electron
in d x2 _\,2) and VO(IV) (unpaired electron in dx.J, the condition of strict orthogonality for the interaction
between the magnetic orbitals d x 2 -\' 2 (CUll) and dry
..
(VI V) is maintained. It leads to a 90° ferromagnetic
exchange. These are compared and illustrated in Fig. 8.32.1.4. A similar condition of strict orthogonality
between the magnetic orbitals of Cu(ll) and Cr(lll) in the corresponding heterometallic dimer is
attained.
** When the LCu-O-Cu bond angle is much larger than 90°, an antiferromagnetic superexchange
predominates but when the bond angle is close 90°, a ferromagnetic exchange predominates (cf
Sec. 8.31.2).
* Cases of accidental orthogonality and strict orthogonality: In the CU202 ring, for
ry
LCu-O-Cu = 90°, the superexchange process involving the metal magnetic orbitals d x2 _ i
and p-orbitals of the bridging O-site leads to the zero overlap integral causing a ferromagnetic
ra
exchange (see Fig. 8.28.4.2c). This is a case of accidental orthogonality of the magnetic orbitals.
ib
In fact, the d 2 2 magnetic orbitals are of the same symmetry and these two orbitals are not
x -v
orthogonal. The word "accidental" has been used to mean that the total overlap integral has been
yl
zero because of the participation of Px and Py orbital of the bridging atom (cf Sec. 8.31.2 and Figs.
8.28,4.2c, 8.29.2.1, 2). However, in the heterometallic dimeric core 'CU02V', the magnetic orbitals
m
d x 2 -.i and dxy are strictly orthogonal (i. e. overlap integral is zero) to cause the ferromagnetism.
he
8.32.2 Dinuclear Complexes ofTitanium(lIl)
Ti(lll) is a 3d l system. In the dimeric forms of bis(pentahaptocyclopentadienyl)titanium(lll) halide i.e.
lc
. X
. (T\ S -e SH S )2 Ti( )Ti(T\ S -e sH S )2 where X- = 0-, Br- and
ea
1- acting as the bridging ligands, the
X
antiferromagnetic interaction (negative 1 value) between the Ti(lll) centres is attained through the direct
th
Ti(III)-Ti(lll) interaction (cf dxy-d.ty a-overlap, Figs. 8.32.1.3, 4).

e/
8.32.3 Single Oxido-bridged vs. Hydroxido-bridged Dinuclear Complexes of

Chromium(lIl) (ct. Sec. 8.28.5a for 180 superexchanges in d3 systems)
0
t.m
Relative efficiency of the oxido bridge and hydroxido bridge in antiferromagnetic superexchange
interaction: The magnetic properties of the oxido-bridged complex, [(H 3 N)sCr-O-Cr(NH 3 )s]
Br4 (21 = -180 em-I) and the hydroxido-bridged complex, [(H 3N)sCr-OH-Cr(NH 3)s]Brs (21 =
e
-15 em-I) are quite interesting to compare. In the oxido-bridged complex, the Cr-O-Cr linkage is
er
linear while in the hydroxido-bridged complex, the Cr-OH-Cr linkage is angular (-120°). It indicates
that the oxido-oxygen uses the sp hybrid orbitals for making the Cr-O-Cr linkage while the hydroxido-
H
oxygen uses the Sp2 hybrid orbitals for making the Cr-OH-Cr linkage. The d 3-Cr(lll) centre bears the
three unpaired electrons in t2~' For that d 3-systems, the efficient a-type 180 superexchange interactions
0
k
cause the antiferromagnetic interactions. These are:

lic
e~ ~ p; p; p;
~ t~g ; e~ ~ ~ e~; t~g .1 .1 t~g (c/. Fig. 8.28.4.1c and Sec. 8.28.5a)
These are discussed in detail for the d 3 i.e. ~g systems in Sec. 8.28.5a (case of CaMn03)' These 180°
C
superexchange paths bring about the antiferromagnetic interaction for the CrIlI-O-CrIlI segment
having the bond angle close to 180°. Besides these a-type 180° superexchanges, the 1t-type 180°
superexchange interactions can also cause the antiferromagnetic interactions. These 180° superexchanges
(leading to the antiferromagnetism) cannot efficiently occur for the CrIlI-OH-CrIIl segment having
the bond angle significatly deviated from 180°. The routes of 1t-type 180 superexchange paths for the
0
CrIlI-O-CrIlI and CrIlI-OH-CrIlI systems are discussed and compared below.

If the Cr-O-Cr linear linkage (-180°) lies along the z-axis (i.e. use of the SP: hybrid orbitals of the
oxido-oxygen) then the P.; and p~ filled orbitals of the bridging oxido-oxygen can particitate in the
1t-type interaction with the dx~ and dy~ orbitals of CrIll respectively.
. l(cr III )d 1 ~ x2 (O)~dl (Cr III )) 180° superexchange leading to

cf Figs. 8.28.3.5,
8.32.3.1
x:
(Cr )d~:
lII
+
(tt) P (tt) x: an antiferromagnetic exchange.
p; (O)+d:,: (Cr lll
) ('1.. denotes non-orthogonality).
Thus in the oxido-bridged species, two filled p-orbitals of the bridging oxygen are available for the
superexchange interaction while in the hydroxido-bridged species, only one filled p-orbital is available
ry
for such a 1t-type superexchange interaction. Thus it is reasonable to expect that the antiferromagnetic
superexchange interaction in the oxido-bridged species is more efficient than that in the hydroxido-
ra
bridged species. In fact, it is supported by the i-values.
•
ib
yl
m
he
lc
ea
th
e/
+
t.m
Fig. 8.32.3.1 Schemetic representation of 180 TC-type superexchange, i.e. (Cr)d.~.~

0
p~ (O)+d.~.~ (Cr)
(= 3c - 4e bonding, TCfiMO TC~BMO TC~BMO' cl Sec. 8.29.1 B).
It is evident that the 180° 1t-type superexchange becomes less favoured with the bending of the
e
Cr-O-Cr linkage. Thus in the hydroxido bridged complex where the bond angle (-120°) is
er
significantly deviated from 180°, the 1t-type superexchange pathway is less efficient. Thus in the
hydroxido bridged complex, the antiferromagnetic interaction is less favoured because of the
H
following reasons.
(i) efficient 180° (a-type) superexchange pathways bringing about the antiferromagnetism
k
are important for the linear Cr-O-Cr linkage but these paths become inefficient for the bent
lic
Cr-OH-Cr linkage.
(ii) two 180° n-type superexchanges produce the antiferromagnetism in the oxido-bridged
C
complex while in the hydroxido bridged complex only one such n-type superexchange pathway
exists.
(iii) bending of the Cr-O-Cr linkage in the hydroxido bridged complex makes the both the 180 0 (j-
and 1t-type superexchanges less efficient.
It may be noted that the direct t 2g- t2g C1-type overlap, e.g. (Crlll)d.~y- d~r.iCr(lI) to cause an
antiferromagnetism (c:f Figs. 8.32.1.3-4) is possible when the Cr-O-Cr bond angle tends to 90°.
Such a situation does not arise for the single oxido-or hydroxido bridged binuclear complex.
Note: To explain the diamagnetic property of oxy-hemerythrin consisting of a binuclear
Fe(III)-core, it has been suggested that it is - 0 - bridged not -OH- bridged.
8.32.4 Strong Antiferromagnetic Interaction in Dimeric Chromium{lI) Acetate

Monohydrate
[Cr(CH3C0 2)2(OH2)]2 has a structure similar to that of dimeric copper(II) acetate monohydrate (L.'f.
Fig. 8.31.1.1, Sec. 9.19,12-8 of Vols. 2 and 3). In this dimeric complex of Cr(II), the Cr-Cr distance
(236 pm) is smaller than the Cr-Cr distance (250 pm) in the metallic chromium. In fact, in the present
complex of Cr(II), there is a quadruple bonding between the Cr(II) centres. The bondings can be
ry
realised from the electronic configuration of high spin Cr(II), i. e. fig egl • Due to the z-out Jahn-Teller
ra
distortion, the unpaired electron in the eg level is housed in the dz. 2 -orbital. Thus the electronic configu-
ration of Cr(II) is:
ib
yl
Assuming the Cr-Cr bond to remain in the z-direction, the following bonding interactions will
m
occur.
cr IT IT 8
he
d:. 2 -d: 2 , d x : - dx:.' d y:. - dy :., d xy - dxy
i. e. 10' bond, 27t bonds, 1l) bond.

lc
This quadruple bonding (cr;;nt (~F) can explain the diamagnetic (21 = -400 cm- I) character of the
ea
complex. The Cr-Cr· bond energy (-45 kJ mol-I) is also fairly high. It may be noted that in the
corresponding Cu(II) complex, the antifeITomagnetic coupling (21 = -295 cm- I) is relatively weaker
th
(ef Sec. 8.31.1) and the cu-eu bond is also relatively weaker.
z
e/
/ /o~r~/o,~
t.m
//: Cr : "~
... ::,>0(//1
HC 1:'/ """: \ C - - CH
~'"?~
e
3 - 3
C-,I, '0·········· :: " ,"

er
/
/I' II ·········0
H3
,.
~~®II
Cr
/~/;
: /
-CH 3
H
,:/ ~. y
'~b··········· I··········0
/
:/I' x
k
lic
8 - bonding
OH 2
d~y- d~y
C
a*---
7t*---
8*---
8b 1~
7t b -%- 1b
a --4b--
b
Fig. 8.32.4.1 Quadruple bonding in [Cr(CH 3C0 2 h(OH 2)h.

8.32.5 Diamagnetic Character of [Mn 2(CO)10]

Mn(O) may be considered to undergo J2 Sp3 hybridisation. The seven valence electrons of Mn(O) are
distributed as follows:
1~
--- --- ---
1~ 1~
L________ __------J
ry
~
3d d2sp3
ra
The three unhybrid d-orbitals (i.e. d xy , d y: and d:x ) house three paired spins and the seventh electron
is housed in one of the hybrid orbitals. The remaining five hybrid orbitals are utilised for binding the
ib
5 CO groups. Thus each Mn(CO)5 fragment bears an unpaired electron in a cP Sp 3 hybrid orbital.
yl
Overlap between these two hybrid orbitals of two adjacent Mn(CO)5 fragments produces a bond between
the Mn-centres.
m
he
lc
This Mn-Mn bonding leads to spin pairing and it explains the diamagnetic character of [Mn2(CO)1O]'
ea
8.32.6 Other Examples of Metal-Metal Bonding Leading to an Antiferromagnetic
Coupling
th
Several examples like [Re2CIs]2-, [M0 2CI g]4-, [Re2(RC02)2X4], [Re3X9]' [M06BrS]4+, etc. have been
discussed in Secs. 9.19 and 12.8 (of Vol. 2 & 3). Quadruple bonding in [Re2CIs]2-leads to a diamagnetism
e/
(ef Fig. 8.32.6.1).

t.m
/ 1CI CI
/ CI
// 1
C~ - ___ // 1
1 + / 1
e
1 / I
I 1- R - - __ ' :
er
: - ~ ~--J..
1 /{/: I ,+, .-- <1 1
1 // I y/' , 1 ,CI I
91 '~
H
I 'I '// I
CI- - - _I ' / <J... I
+ J. "
/1
1-..<"
--~""" L,/ 'I I
/ I' 't
k
/ I --_ I'
: + ---'CI'
lic
1
I /
CI CI CI
C
Fig. 8.32.6.1 The quadruple bonding in [Re2CIRf-
Note: For details of the bonding, see Sec. 9.19 of Vol. 2).
8.32.7 Diamagnetism in [M 20X 10]4- (X =CI, Br; M =Ru or Os)

In this group, the classical example is K4[Ru20CllO] which is diamagnetic. Ru(IV) (d4 system) remains
in the octahedral field having the electronic configuration (2; (low-spin). Assuming the electronic
configuration as dx~' dx~ dy~ and Ru lV-O-Ru IY linkage along the z-axis we can have the following
a-type and 1t-type 180 superexchange antiferromagnetic interaction.
0
I/
CI
C I - Ru1v-O- Ru1v-CI
C1
CI
I/ C1
t
x-axis .
CI
/1 CI
CI/ICI Lz-ax,s
ry
(R )d l cr 2 (0 2- ) cr dl (R )}(cf Figs. 8.28.4.1c, 8.32.1.1 b)
u x,: ~ Pz. ~ x;: u a - type 180 0 superexchange (GKA rule)
ra
(Ru)d~z+p;(02-)+d~z(Ru)(= 3C-4ebOnding ))(cf Fig. 8.32.3.1)
ib
(Ru)d l._ ~P~ (0 2- )~dl._ (Ru)(= 3c-4e bonding) (180 It - type superexchange)
0
.1... (n:).1 (n:) .\..:.
yl
In each 180 0 1t-type superexchange, participation of 3 orbitals (two metal d-orbitals and one bridging
m
ligand orbital) produces three three-centred MOs (1 BMO + 1 NBMO + 1 ABMO). Four electrons are
placed in the BMO and NBMO (cf Sec. 8.29.1B).
he
8.32.8 Antiferromagnetic Interaction in KMF 3 and K2 MF4 (M =bivalent transition
metals) and Transition Metal oxides (cf. Secs. 8.28.5)
lc
Antiferromagnetism in KMF 3 is attained throughout the lattice. It is due to the linear-M-F-M-
ea
bond where the filled pcr-orbital of the bridging fluoride can participate in 180 0 superexchange
(antiferromagnetism) with the t 2g orbitals of the metal centre (cf Figs. 8.28.4.1 c and 8.32.1.1 b). The
filled pcr-orbital of the bridging fIouride can also participate in a-type 180 0 superexchange with the
th
unpaired electrons in the ex orbital of the metal centre (Fig. 8.28.3.4) «(f magnetic properties of MO,
e/
e.g. MnO, cf Fig. 8.28.5.4).

The different possible 180 0 superexchange pathways leading to the antiferromagnetism in MnO
t.m
have been discussed in Sec. 8.28.5 in detail. These are:

a-interaction: (M)d~2 - P; (0 2 -) - d: 2 (M); (M)d.~2_y2 - Px (0 2 -) - d_~2_y2 (M) (cf Fig. 8.28.3.3.4)
a-interaction: (M)t~g - Po (0 2-) - t~g (M); e.g. (M)d.~z + P; (0 2-) + d_~z. (M) (cf Fig. 8.28.4.1)
e
P;
1t-interaction: (M)d.~, + p.~ (0 2 -) - d.~y (M); (M)d;z + (0 2-) - d.~z. (M), etc. (cf Fig. 8.28.3.5)
er
These 180 1t- and a-type superexchange processes leading to the antiferromagnetism can also be
0
explained in terms of 3c-4e bonding (MOT, Sec. 8.29.1). The following a-type 180 superexchange 0
H
(Figs. 8.28.4.1, 8.32.1.1b) process leading to an antiferromagnetism (GKA rule) is illustrated in Fig.
8.32.8.1.
k
lic
C
~ -+---<~I---. .
• => Mn
o => 0
Mn Mn
1------0----
(b)
(a)
Fig. 8.32.8.1 (a) Antiferromagnetic MnO crystal (below 122 K); (b) Antiferromagnetic interaction in MnO crystal
through a a-type 180 0 superexchange path.
The 1t-type 180° superexchange path bringing about the antiferromagnetism is illustrated in Fig.
8.32.8.2.
ry
ra
.~
ib
d-orbital
p-orbltal
(t 29 - orbital)
yl
@ = Metal e =Oxygen
m
Fig. 8.32.8.2 Antiferromagnetic interaction in the transition metal oxide (MO) crystal through the n:-type 180 0 super-
exchange path ((f Fig. 8.28.3.5).
he
8.32.9 Antiferromagnetic Interaction in some Metallobiomolecules
lc
Iron-sulfur protein [2Fe - 28]: It can act as a one electron transport agent. In the oxidised form, both
the iron centres are tetrahedral Fe(III) (e 2tl) while in the reduced form, one is Fe(III) (e 2ti) and another
ea
one is Fe(II) (e 3t2'). The oxidised form is diamagnetic (5 =0) and the reduced form is paramagnetic with
respect to one unpaired electron (5 = 1/2). It indicates the strong antiferromagnetic interaction between
th
the metal centres in both the oxidised and reduced forms.

e/
cys-s" / s" / S-cys

Fe Fe
t.m
cys-S / '"S / ' " S-cys
1\
In the oxidised form (diamagnetic and epr silent), the Fe-Fe distance is 270 pm with Fe- S -Fe
e
angle ca. 75° and the Fe-Fe distance in the reduced form is 276 pm. In the reduced form, the odd
er
electron is delocalised over the both sites. The short Fe-Fe distance supports the presence of
significant metal-metal bonding leading to an antiferromagnetic spin pairing. Here it may be
H
mentioned that the filled p-orbitals of the bridging sulfur also participate in the superexchange process
(ef. CuzOz ring, CrZ03 ring; Sec. 8.31.2) to some extent to bring about the antiferromagnetic inter-
k
action between the metal centres.

lic
(Note: Antiferromagnetic interaction in the dinuclear and polynuclear iron and copper
metalloproteins, has been discussed in the author's book, Bioinorganic Chemistry, Books & Allied,
C
Kolkata).
Sometimes, in the mononuclear complexes, an antiferromagnetic coupling interaction may occur in
between the unpaired electrons of the ligand and metal centre. Such examples are: oxy-myoglobin,
oxy-hemoglobin, brown ring complex or nitropruside (ef. Fig. 11.16.3.4, Vol. 2 of this book).
8.33 SOME SPECIAL CASES OF COOPERATIVE MAGNETISM: FERRIMAGNETISM,

CANTING ANDWEAK FERROMAGNETISM (ct. Sec. 11.1.6.3, Vol. 2)
Alignment of spins of the magnetic centres in different classes of magnetic substances is shown in Fig.
8.33.1.
1rill rill \ 1--.1 \ I1III (a)
ry
iiiiii i !i ! i ! i~i~i~
ra
ib
(b) (c) (d)
yl
m
(e)
he
Fig. 8.33.1 Alignment of individual magnetic dipoles in (a) paramagnetic, (b) ferromagnetic, (c) antiferromagnetic and
(d) ferrimagnetic, (e) canted antiferromagnetic substance.
lc
ea
8.33.1 Ferrimagnetism
In the case of ferrimagnetism, the spins are opposed but the magniduces of the opposing spins are not
equal. In fact, in a ferrimagnetic substance, two nonequivalent sublattices tend to oppose magnetically.
th
The inverse spinels AFe204 i.e. Felll(AIIFelll)04 where A = Fe, Co, Ni etc. commonly called ferrites
e/
show the ferrimagnetism. In ferrites, there are two nonequivalent sublattices: octahedral and tetra-
hedral units. In ferrites, the Fe(lll) centres in the tetrahedral sites undergo an antiferromagnetic cou-
t.m
pling with the high-spin Fe(lll) centres placed in the octahedral holes. Thus the resultant magnetic
behaviour of the ferrites is determined by the nlagnetic behaviour of A(II). It can be illustrated for
magnetite Fe304' i.e. Felll(FeIIFeIlI)04. The two sublattices are: Fe(II) (tige;) and Fe(III) (tige,~) in the
octahedral sublattice with the 'Fe06' chromophore and Fe(lll) (e 2t 23 ) in the tetrahedral sublattice with
e
the Fe04 chromophore. The resultant magnetic moment is determined by the magnetic moment of
er
Fe(ll) in the octahedral sublattice.

The ferrimagnetic interaction in the bimetallic core of CuIICr1II leads to the paranlagnetism with
H
respect to two unpaired electrons (cf CUll possesses one unpaired electron, CrIll bears three unpaired
electrons).
k
lic
8.33.2 Canting and Weak Ferromagnetism

In the ferromagnetic and antiferromagnetic substances, parallel and antiparallel spin allignments occur
C
respectively. In general, the spins are of the same magnitude. In the ferrimagnetic substances, the
antiparallel spins of different sublattices a~e of different magnitudes.
If the spins of sublattices are neither perfectly parallel nor antiparallel but are canted, then a special
case of weak ferromagnetism may occur (cf Fig. 8.33.2.1).
The canting angle (a) is of very small magnitude (ca. a few degrees only; 0° ( a > 15°). The spins
of sublattices may remain canted spontaneously without any external magnetic field if the total symlne-
try remains the same in both the canted and uncanted state. If we consider only t~vo sub/affices then the
canted antiferromagnetism and cantedferromagnetism may be represented as ShO~Vll in Fig. 8.33.2.1.
If more than two sublattices are involved in canting then the resultant mayor may not lead to
ferromagnetism. If it leads to ferromagnetism then the phenomenon is called ovet meaning open or
unconcealed [e.g. in Co(CH 3C0 2)2· 4H 20] and if it leads to no ferromagnetism then the phenomenon
is called hidden [e.g. in CuCI 2 · 2H 20].
ry
ra
a
(Canted antiferromagnetism) (Canted ferromagnetism)
ib
(a) (b)
yl
m
•
he
J.lR = 0 J.lR:;t: 0
(Perfect antiferromagnetism) (Canted antiferromagnetism)
(c) lc (d)
ea
Fig. 8.33.2.1 Illustration of canted antiferromagnetism and canted ferromagnetism leading to a weak ferromagnetism
(Note: Here only two different sublattices are considered in canting.)
th
Canted magnetism is known to occur in different oxide minerals, e.g. u-Fe203. In different complexes,
this is also established. For example, in CsCoCI 3· 2H 20 (single chorido-bridged polymeric structure
e/
giving rise to an octahedral coordination around COIl), canted antiferromagnetism is established. Canted
t.m
ferromagnetism is argued to exist in (NBu4)[CuCr(OX)3] where a network of the oxalato bridged Cr(III)
(t2~) and Cu(II) (t2~ ei) magnetic centres exist. The d.~.2_\,2 orbital ofCu(II) bearing the unpaired electron
is orthogonal to the d~y orbital of Cr(III) (cf Fig. 8.32.1.4) and causes a genuine case of ferromagnetism
e
(case of strict orthogonality). But the saturation magnetisation (M..) value indicates the presence of
canted ferromagnetism. If Cu(II) and er(III) centres are in a genuine ferromagnetic interaction, M s
er
should have value 4N A~ (equivalent to 1 + 3 unpaired electrons; 1 unpaired electron from CUll and 3
unpaired electrons from Cr III ); if the centres are in a ferrimagnetic interaction, Ms should have the value
H
2NA~ (equivalent to two unpaired electrons, i.e. 3 - 1 = 2). But the experimental value of M s is 3NA~.
It is probably due to the canted ferromagnetism.
k
lic
8.34 COMPETITIVE INTERACTIONS AND SPIN FRUSTRATION

C
8.34.1 Antiferromagnetically Interacting Spins in a Triangular Arrangement

Let us first consider a tringular system of XYX where the magnetic centres (X, Y, X) are located at the
corners of an isoscele triangle as shown in Fig. 8.34.1.1a.
There are two equal interactions, i.e. Y-X and Y-X (represented by J) and one X-x interaction
(represented by J'). For the sake of simplicity, let us assume that the local spins are the same, i.e. S(X I)
1
"2.
= S(X2) = S(Y) = X I and X 2 denote the positions of two Xs. If both J and J' are considered to be
negative then all the interactions Y - XI' Y - X 2 and Xl - X 2 are antiferromagnetic in nature and
then a case of competition will arise.
Case I (p = ;,)1): It indicates that the Y - X.. Y - X2 antiferromagnetic interactions are stronger
than the Xl - X 2 antiferromagnetic interaction. The stronger Y - Xl and Y - X 2 interactions will
enforce the spins of X 1 and X 2 to be aligned in parallel though the antiferromagnetic interaction
between Xl and X 2 will try to oppose their parallel allignment (ferromagnetic interaction). However,
ry
the ratio JIJ' ) 1 will lead to a ferromagnetic coupling between the spins of S(X l ) and S(X 2), i.e.
E(~,I)<Cf. Fig. 8.34.1.1b).
ra
S(X j ) + S(X 2) = 1. Thus the ground state may be represented as
ib
y
yl
m
he
®x
+ ·x
®
)
lc ---v-
1
E(2'O)
ea
(a) (b) (c)
J
th
Fig. 8.34.1.1 (a) Competition among the spins in a triangular system; (b) Ground state when p = ---, > 1; (c) Ground
J
J
state doubly degenerate for p =---, < 1
e/
J
Thus ferromagnetic polarisation of the S(X.) and S(X2) spins are directed by the stronger
t.m
V-Xl and Y-X 2 antiferromagnetic interactions..
Case II (p = ;, (1 ) : It indicates that the X -X antiferromagnetic interaction is stronger than the

l 2
e
Y-X 1 and Y-X 2 antiferromagnetic interactions. Thus the spins SeX 1) and S(X 2 ) will be aligned
er
antiparallel. It will cause one Y-X interaction (i.e. Y-Xl or Y-X 2) to be ferromagnetic and the other
Y-X interaction to be antiferromagnetic. Thus we can write S(X I ) + S(X 2 ) = 0 (i.e. antiparallel
H
arrangement leading to an antiferromagnetic interaction) and the corresponding ground state is E(~, 0 J
k
(cf. Fig. 8.34.1.1c).

lic
The case may be analysed to determine the fate ofY-spin with respect to the spins of Xl and X2 which
remain antiferromagnetically coupled. The spin ofY is frustrated because both the orientations (up or
C
down) will give the same energy and the Y-spin cannot simultaneously participate in the antiferromagnetic
interactions with the spins of Xl and X 2 • Both the orientations (i.e. up or down) of Y will lead to the
same energy and thus the ground state is twofold degenerate. Thus it is a case geometrical frustration.
Case III (p = ;, =1) : Here all the possible three antiferromagnetic interactions along the edges of
the triangle are equally strong. In this triangular arrangement, if the two spins are antiferromagnetically
oriented, the third spin becomes frustrated (Fig. 8.34.1.2) because it cannot simultaneously participate
in the desired antiferromagnetic interaction with the other two spins. Its upward or downward orientation
will lead to one ferromagnetic interaction and another antiferromagnetic interaction. Thus the ground
state (resultant s = ~) is two fold degenerate. In the excited state (i.e. resultant S = %) ,all the three
spins will remain parallel. It is illustrated for the triangular trinuclear complex of Cu(II), Le. Cu!I-system.
ry
. (Frusted spin)
~)
ra
• Ground state ( S = two fold degenerate.
J J
ib
3
• Excited state (S ---2 )
yl
l'-----J------I.j
m
he
Fig. 8.34.1.2 Spin frustration in the case of triangular arrangement of spins antiferromagnetically interacting.
Triangular trinuclear complex of Cu(II), i.e. Cujl cluster «(j: Appendix VIII-F): In such systems,
lc
when the Cu(II) centres are placed at the corners of an equilateral triangle, two of three unpaired
electrons are paired up (i.e. anti parallel arrangelTIent). Thus only the spin doublet state (= 2 x J.- + I = 2)
ea
2
.IS populated ((f S\ + S., + S~ 1 Actually, we can have the resultant S
=-). 1 -,
=-'-, 1 -3 an d t he two Ii0 ld
. 2- 222
th
degenerate ground state is given by S = J.- . In such systems, considering the spin doublet ground
2
e/
state to be populated only at room temperature, f.l is given by:

t.m
., I 2 1 :2 1 :2 • ?)]1/2
J.l ~ ="3Jl1 + "3Jl2 + 3Jl~, i.e. Jl = [ "31 (?,..,
0- + O~ + 1.73- ~ 1.0 B.M.
(c:f f.l2 follo\\J's the additive property). This has been illustrated in Appendix VIII-F.
e
8.34.2 Antiferromagnetically Interacting Spins in a Tetrahedral Arrangement: A Spin

er
Frustrated System
H
In the tetrahedral arrangement of four spins, there lTIay be six interactions along the edges. If all the
interactions are considered to be equally strong then it is not possible to arrange the four spins to
k
produce the six antiferromagnetic interactions. Out of the six possible interactions, four interactions
lic
will be antiferromagnetic (i.e. favourable interactions) while the remaining two interactions will be
ferromagnetic (i.e. unfavourable interactions) (Fig. R.34.2.1). Thus the system is frustrated because
C
it cannot enjoy simultaneously all the possible interactions favourable (i.e. antiferromagnetic). The
ground state (characterised by 4 antifen'omagnetic interactions and 2 ferromagnetic interactions) can be
obtained in different ways, i.e. the ground state is many-fold degenerate.
Characteristics of spin frustration

• Lowest energy state can be obtained in more than one way of spin arrangement.
• The ground state is many-fold degenerate «(f in the unfrustrated state, the ground state singly
degenerate).
• Frustration indicates the inablity of a system to remain in a singly degenerate ground state.
(1,2) and (3,4): ferromagnetic interaction.

Other interactions: antiferromagnetic
ry
ra
~ (4)
ib
yl
Fig. 8.34.2.1 Spin frustration in the case of tetrahedral arrangernent of spins antiferromagnetically interacting
m
8.34.3 Examples Experiencing the Competitive Interactions
he
In different triangular systems. e.g. [Cr30(acetate)6(OH 2 )3]C1·6H 2 0. (51 =52 =53 =%l
[Fe 30(acetate)6 (OH 2 )JCI. 5H 20 (SI == 52 = 53 =

lc
%i.e.. high-spin Felli-centres)cFig. 8.34.3.1)
ea
+
~
o CH 3
th
0
HP~ 1/0'--"'0, I ,/'OH, o
~
0 I
e/
C
/M~ / M"
o I 0 I "0 /-~
t.m
( ~-(h,l(03)
0 1
'·0
~~I ° (M = Cr, Fe)

e
OH 2
er
Fig. 8.34.3.1 Structural representation of [MJO(02CMe)(OH2hl+

H
k
lic
1
C
Fig. 8.34.3.2 Cornpetitivc Inagnetic exchange interactions in the tetranuelear corc. Fe~1I (Jl 3-O)2 of
[Fe~" O/acetate)7 (bpY)2 1+. J = -90 ern-I, l' 2:: -30 cnl- I • i.e. ferromagnetic polarisation along the spine and
antiferromagnctic interaction along the wings.
EXERCISES
A. General Type Questions

I. Define and illustrate the following terms used in magnetochemistry.
pole strength, magnetic induction and Gauss's law, magnetic susceptibility, permeability,
paramagnetism, diamagnetism, ferrimagnetism, ferromagnetism, canted ferromagnetism, canted
ry
antiferromagnetism, Curie's law, Curie-Weiss law, Langevein-Debye equation, isomorphous
ra
dilution, diamagnetism and Lorenz's law, diamagnetic susceptibility and Pascal's constant, Lande-
interval rule, spin-orbit coupling constant, Van-Vleck equation, Bleany-Bowers equation, 1st order
ib
and 2nd order Zeeman effects, TIP, Kotani expression.
2. Show the following relations:
yl
P = 1+ 41tXv' Il m = 2.83JXMT B.M.
m
Il m = 797.6JXMT B.M. (SI system), XM = 41t(1.68 X 10-9 ) S(S + 1) m 3 mol-I
he
XM = 1.68 X 10-3 S(S + l)cm 3 mol-I, 1 B.M. = 9.274 x 10-24 J T- 1
I B.M. = 9.274 x 10-21 erg 0- 1, III = ~ ---.!.!!.- lc
41tmc
ea
Il s = ~4s (s + I) ---.!.!!.-, Ys /Y I = 2.0
41tmc
th
3. Compare the properties of different types of magnetic substances.

e/
4. Discuss the origin of diamagnetism and characteristics of the diamagnetic substances.

5. Illustrate Pascal's law to compute the diamagnetic susceptibility.
t.m
6. Discuss the principle and procedure for determination of magnetic susceptibility by Gouy's method.
Mention the drawbacks of the method.
7. What is the origin of 8 (Weiss constant) in Curie-Weiss equation?
e
8. What do you mean by spin-orbit coupling constant? Discuss the factors to determine the magni-
tude of spin-orbit coupling constant.
er
9. What do you mean by Lande interval rule? Illustrate the rule for J2 and d 8 systems.
H
10. What do you mean by multiplet width? Discuss the dependence of paramagnetism on the relative
values of multiplet width (~EJ.J+I) and thermal energy (kBn in the following cases.
~EJ.J+I ~ kBT, ~EJ.J+I » kBT, ~EJ.J+I << kBT.
k
11. Discuss the effect of external magnetic field on the splitting of energy levels.
lic
12. What do you mean by 1st order and 2 nd order Zeeman effect? Illustrate.
13. What is the Bose-Stoner equation to calculate J.lt:ff?
C
14. Discuss the conditions for orbital contribution to J.l~ff. Orbital contribution is very often quenched
in the complexes-why?
15. What do you mean by g (Lande splitting factor)? Calculate the g-value for a free electron and a
free gaseous halogen atom.
16. Discuss and compare the possibility of orbital contribution to J.leff' in the octahedral, tetrahedral,
square planar and square pyramidal complexes.
17. Discuss the possibility of orbital contribution to J.leff from the excited states through the spin-orbit
coupling.
18. Compare the magnetic properties of A, E and T ground state terms.
19. Spin-orbit coupling contribution to J..leff is less significant for the low-spin and strong field complexes.
Explain.
20. Discuss the temperature dependence of J..leff for the A, E and T ground state terms.
21. Give the conditions for mixing of the ground state with the excited state via 2nd order Zeeman
effect.
22. Discuss the characteristic features of 2nd order Zeeman effect and its contribution to XM.
ry
23. How can you determine the spin-orbit coupling constant from the measurement of J..leff?
24. Give the expressions of XM(Total) and J..leff arising from both the 1st order Zeeman effect (including
ra
the spin-orbit coupling contribution) and 2nd order Zeeman effect for the E- and T-terms.
25. Discuss the significance of orbital reduction factor (k).
ib
26. Discuss the magnetic properties of the octahedral and tetrahedral complexes of the 1st transition
yl
series metal ions.
27. Discuss the magnetic properties of Fe(II), Co(II), Ni(II) and Cu(II) complexes in terms of orbital
m
contribution from the both ground and excited states.
28. Discuss the magnetic properties of the lanthanides.
he
29. Discuss the magnetic properties of Eu(III) and Sm(III).
30. Compare the magnetic properties of the (i) lanthanide complexes and complexes of 1st transition
series; (ii) lanthanide and actinide complexes. lc
31. Discuss and compare the temperature dependence of the magnetic properties of the ground state
ea
characterised the by the A, E and T-terms.
32. Discuss the temperature dependence of J..leff of the 1st transition series complexes with the
th
T-ground state terms.

33. How can you calculate the L-value of T-terms? Illustrate with examples.
e/
34. How do you calculate the g-value of a particular J-Ievel arising from a T-term? Illustrate with
examples.
t.m
35. Show the spin-orbit coupling splitting of the 2T2g term arising from the 2D state (i.e. t2~ electronic
configuration).
36. What do you mean by Kotani plot? Illustrate for the lighter and heavier transition metal ion
e
complexes.
er
38. Discuss the temperature dependence of f.!eff for the octahedral complexes of Ti(III) and tetrahedral
complexes of Cu(II). In both cases, the ground state term is 2T.
i
H
39. Discuss the temperature dependence of the magnetic moment of t2~ and t 2 configurations char-
acterised by the 3T1g term.
40. Discuss the magnetic properties of the complexes of 2nd and 3rd transition series in comparison
k
with those of the 1st transition series.

lic
41. Discuss the characteristic features of the 2nd order Zeeman effect contributing to the magnetic
susceptibility.
C
• Generally it leads to TIP but in some cases this may not be true.
42. Give the expressions of XM(2nd order) for the A and E ground state terms.
43. What do you mean by delocalalisation factor or orbital reduction factor (k)? What does it signify?
How can you determine this factor from the magnetic data?
44. What do you mean by thermal equilibrium between the high-spin and low-spin state in the cross-
over region? Illustrate with examples. Give the conditions for the occurrence of such spin-isomerism.
45. Discuss the high-spin ~ low spin isomerism in terms of the potential energy diagrams.
46. Discuss the factors controlling the magnitude of pairing energy.
47. How can you explain the spin-state isomerism in terms of the Tanabe-Sugano diagrams?
48. Discuss the effect of pressure and temperature on the equilibrium involving the spin state isomerism.
49. Give the expressions of XM(obs) for the d 5 and d 6 systems remaining in an equilibrium involving
the spin state isomerism (h.s. ~ l.s.).
50. Discuss the charateristics of different types of spin transition curves.
51. Discuss the spin state isomerism in the Fe(II), Fe(III), Co(II) and Co(III) complexes.
52. Discuss the spin state isomerism in the Ni(II) complexes.
ry
53. Discuss the spin state isomerism in the square planar complexes.
56. Discuss the possibility of spin state isomerism in the five coordinate complexes of trigonal
ra
bipyramidal and square pyramidal geometries.
57. Discuss the magnetic properties of the intermediate spin and spin-admixed states in the square
ib
pyramidal and square planar complexes.
yl
58. Give the examples of thermally controlled spin equilibrium involving an intermediate spin.
59. Give the structural isomerism leading to the spin state isomerism, anomalous magnetic property
m
and electronic spectra.
60. Discuss and illustrate the equilibria: (i) octahedral ~ tetrahedral; (ii) square planar ~ tetrahedral;
he
(iii) octahedral ~ square planar; in terms of the electronic spectra and magnetic properties.
61. What do you mean by intrallogons?
lc
62. What are the different types of spin isomerism? How do you distinguish these?
63. What do you mean by an anomalous magnetic moment? What are the different causes of this
ea
phenomenon?
64. Discuss the normal range of Jleff for the Fe(III), Fe(II), Co(II), Ni(II) complexes.
th
65. What do you mean by ferromagnetism, antiferromagnetism, ferrimagnetism and canted magnetism?
66. What are the possible routes of antiferromagnetic interaction?
e/
67. Superexchange pathway may lead to both ferromagnetism and antiferromagnetism-explain and
t.m
illustrate.
68. What do you mean by Goodenough-Kanamori-Anderson rule (i.e. GKA rule)? How can you
explain the origin of ferromagnetic and antiferromagnetic exchange in terms of GKA rule.
69. Illustrate the 180° and 90° superexchange in terms of GKA rule? How can you explain the results
e
in terms of molecular orbital bonding?

er
70. Apply GKA rule to explain the magnetic properties. MnO, CaMn03' NiO, NiCI 2, MnC1 2, CrC1 3,
CuCI 2, and CoCl 2 crystals.
H
71. The nature of superexchange interaction in the segment, M-L-M depends on the bridge angle.
Explain in terms of the MO treatment.
k
72. Critically comment on the mechanistic paths of antiferromagnetic interaction in CU2(CH3C02)4'

lic
2H 20.
73. There are strong evidences that the antiferromagnetic interaction in CU2(CH3C02)4' 2H 20 occurs
C
through the superexchange path. Explain.

74. Discuss the temperature dependence of XM and Jleff of CU2(CH3C02)4' 2H 20.
75. Discuss the antiferr<;>magnetism in different types of dinuclear complexes of Cu(II).
76. Discuss the magnetic properties of the following type di-hydroxidobridged dinuclear Cu(II)
complexes depending on the bridge angle (a).
( N", A /N)
Cu a Cu
~
N N = bpy, phen, tmen, teen, etc.
N/ "'0/ "'N
H
77. Discuss the magnetic properties of the followings:

H 0 0
(( L{
L1dll/O",,-c;,fL)~ ;_ ~~O-~O~;
""-~/ "L /2 / I / I
Fe S -ferredoxin.
2 2
ry
(Me in +5 state)
ra
ib
; Oxy-hemerythrin.
yl
m
(Me in +5 state)
he
o
"- ~O"",II/' lc
/cu /v"-
ea
"'0/
th
78. Discuss the ferrimagnetism of ferrites.

e/
79. Discuss the canting and weak ferromagnetism.

t.m
80. Illustrate the competing interactions among the spins and spin frustration for (i) triangular ar-
rangement of spins, and (ii) tetrahedral arrangement of spins.
81. Regular and distorted tetrahedral geometries of the Ni(II) complexes can be identified by meas-
uring the magnetic moment data-illustrate.
e
82. Derive the following relations and equations:

er
(i) Jl when ~j, j + 1 ) kBT; t £ j , j + 1 ( kBT; t £ j , j + 1 ==:: kBT; (ii) Curie equation, (iii) van-Vleck
equation; (iv) Bleany-Bowers equation for the dinuclear and trinuclear complexes; (v) Lande
H
interval rule; (vi) spin interaction energy; (vi) Kotani expression.
B. Justify the following statements:

k
lic
1. Jleff of K2 [ReI6] increases from 3.32 to 3.55 B.M. when the solid is dissolved in water.
2. When K2 [OsCI6 ] crystals are diluted with the isomorphous diamagnetic crystals of K2 [PtCI6 ] , the
C
magnetic moment increases from 1.44 B.M. to 1.94 B.M.

3. Though the origin of diamagnetism lies in all,types of substances, it is only noticeable when the
substance contains the paired electrons and no unpaired electron.
4. Diamagnetism is independent of temperature.
5. Diamagnetic susceptibility follows the law of additivity along with the constitutive corrections.
6. 2nd order Zeeman effect very often leads to the temperature independent paramagnetism (TIP).
7. Mn04" or CrOl- is characterised by the tfJ system but there may be some weak paramagnetic
property.
• There is no unpaired electron in Mn04" or CrOl-, but they are weakly paramagnetic.
8. In the presence of a crystal field, orbital contribution to the magnetic moment is very often
quenched.
9. For a free electron, the g (Lande splitting factor) value becomes 2 but the g-value depends on the
chemical environment when the electron is considered in a compound.
10. In the octahedral complexes, the unsymmetrically filled t 2g level can make an orbital contribution
to J.leff.
ry
11. Compared to the square planar complexes, possibility of orbital contribution to J.leff in the octahedral
complexes is more.
ra
12. J.T. distortion reduces the possibility of orbital contribution to J.leff.
ib
13. The low-spin square planar complexes ofCo(II), e.g. [Co(salen)] (J.leff= 2.25 B.M.), [Co(bigH)2]S04
(J.leff = 2.70 B.M.) show the magnetic moments higher than J.lspin (= 1.73 B.M.) though the orbital
yl
contribution is not expected.
m
14. The square pyramidal complexes (C 4v symmetry) of Co(II) very often show J.leff) J.lspin (= 1.73
B.M.).
he
15. Magnetic moments of the square pyramidal complexes of Ni(III) and Co(II) are different though
both of them are having the same d7 configuration.
16. Orbital contribution to J.lobs occurs for the octahedral complexes of Ti(III), V(III), low-spin Mn(III),
lc
low-spin Fe(III), high-spin Fe(II), high-spin Co(III), and high-spin Co(II).
ea
17. Ground states characterised by the T-term can make an orbital contribution to J.leff.
18. Ground states characterised by the A and E terms fail to make an orbital contribution to J.leff.
th
19. Sometimes, the excited states can make an orbital contribution to J.leff through the spin-orbit
coupling.
e/
20. The relation, fleff = (1- l~~q JflsPin is applicable for the A and E ground states but not for the
t.m
T-ground state.
21. For the A and E ground state, J.leff may be greater or less than J.lspin depending on the d n configu-
ration but for the T-ground state, J.leff is always greater than J.lspin.
e
22. Temperature dependence pattern of J.leff for the A and E ground state terms is different from that
er
for the T-term.

23. Orbital contribution from the ground state always makes J.leff ) J.lspin but orbital contribution from
H
the excited state through spin-orbit coupling may make J.leff greater or less than J.lspin depending on
the condition.
k
=g~S(S+I) B.M., depending on the condition, g may be equal 2or 2(I-~J.

lic
24. fleff
IODq
25. Mixing of the ground state with the excited state via the 2 nd order Zeeman effect can occur only
C
under certain conditions.

26. Contribution of the 2 nd order Zeeman effect to XM is generally described as TIP (i.e. temperature
independent paramagnetism) but this contribution may not be always temperature independent.
27. Low-spin complexes of Co(III) show some small amounts of paramagnetism.
28. Spin-orbit coupling constant can be determined from the measurement of J.leff.
29. Magnetic moment of the high-spin complexes of d 5-system is very close to the J.lspin only.
30. XM(TIP) is only accountable when XM(spin) is absent.
31. Orbital reduction factor (k) for both the 1st order and 2 nd order Zeeman effect gives the measure
of metal-ligand covalent interaction and nephelauxetic effect.
32. For the high-spin octahedral Co(II), high-spin octahedral Fe(II), tetrahedral Ni(II) and tetrahedral
Cu(II) complexes, Jlobs is found greater than Jlspin.
33. For the 1st transition metal complexes (octahedral and tetrahedral), the general observations are:
l 4
Jlobs ::= Jlspin (for d - ), Jlobs = Jlspin (for tP), Jlobs ) Jlspin (for cf'-9).
34. For the A and E ground state, contribution of the spin-orbit coupling interaction to Jleff is quite
straight-forward.
ry
35. For the Fe(II) complexes, Jlobs is higher than Jlspin, i.e. Jlobs ) Jlspin.
36. For the Co(II) complexes:
ra
Jlobs: 0h (h.s.) ) Td ) 0h (l.s.).
and in all cases, Jlobs ) Jlspin
ib
x-
yl
37 [COX4~-: I I I
. J SCN- I CI- I Br- I I-
m
I I I
- Jlobs: 4.4: (4.6 : (4.7 : (4.8
he
(B.M.)
38. For the different types of Co(II) complexes, Jlobs is deviated from Jlspin but this deviation is
minimum for the low-spin octahedral complexes. lc
39. For the square planar complexes of Co(II), Jlobs is significantly higher than Jlspin.
ea
40. For [COX4]2-, Jleff bears an inverse a linear relationship with the 10Dq value.
41. Jlobs is significantly higher than Jlspin for the tetrahedral complexes of Ni(II).
th
42. From the knowledge of magnetic moment, the regular and distorted tetrahedral complexes of
Ni(II) can be distinguished.
e/
43. For the Ni(II) complexes:

Jlobs: square planar ( octahedral ( tetrahedral.
t.m
44. For the Cu(II) complexes: Jlobs(Td) ) Jlobs( 0h).

45. For the lanthanide complexes, the crystal field effect to quench the orbital contribution is not
important.
e
46. Spin-orbit coupling constants for the lanthanides are high and consequently J appears as a good
er
quantum number.
47. For the lanthanides, Jleff is generally given by:
H
Jleff = JlJ = gJ ~""'-J(-J-+-l) B.M.

but in some cases (e.g. Eu 2+, Gd3+ etc.), it leads to: Jleff = ~4S(S + 1) B.M.
k
48. The magnetic moments of Sm(III) and Eu(III) complexes are not given by Jleff = gJ ~J (J + 1) B.M.
lic
which is in general applicable for the other lanthanides.

C
49. In the case of Eu(III), Jleff ::= 3.5 B.M. (at 300 K) but Jleff calculated by the relation,
Jleff =gJ~J(J+l) B.M. becomes zero.
50. Crystal field effect is more important for the actinides compared to that for the lanthanides.
51. For the 1st transition series, the magnetic properties of the A and E terms are more or less insen-
sitive to temperature variation while for the T-term, Jleff is quite sensitive to the temperature
variation.
52. For the lanthanides, in general, Jleff calculated by 'JlJ expression' is in good conformity with the
experimental findings but for the actinides, the calculated JlJ values are somewhat larger than the
observed values.
53. Among the actinides, in terms of magnetic properties, Pu(lll) and Am(lll) appear as the
exceptions.
54. In terms of magnetic properties, the actinides Pu(lll) and Am(lll) are comparable with the lantha-
nides Sm(lll) and Eu(III).
55. The .ground state term of the octahedral V(III) complexes is 3T1g • Thus, their magnetic moments
should show the temperature dependence but it is not experimentally verified.
ry
• In terms of temperature dependence of Ileffi octahedral complexes of V(III) are the exceptions.
56. For a T-term, the L-value is unity.
ra
57. Octahedral complexes of Ti(lll) are characterised by tig(i.e. one unpaired electron) but at very low
temperature Ileff::::; 0 and at ordinary temperature Ileff is finite and positive (ca. 1.8 B.M.).
ib
58. For the dl-octahedral systems of the heavier transition metal ions, Ileff is very small at ordinary
yl
temperature but at very high temperature the value is saturated to -1.8 B.M.
59. Tetrahedral complexes of Cu(ll) (2T2 term) bearing one unpaired electron per Cu-centre show Ileff
m
::::; 1.73 B.M. at very low temperature and Ileff only slightly increases with temperature.
he
60. Both the octahedral complexes of Ti(lll) and tetrahedral complexes of Cu(ll) are characterised by
the presence of one unpaired electron per metal centre, but for Ti(III), Ileff::::; 0 at -0 K, while for
Cu(II), Ileff::::; Ilspin = 1.73 B.M. even at 0 K.
lc
61. K3[Mn(CN)6] shows Ileff::::; 0 at very low temperature, though there are two unpaired electrons per
ea
metal centre (cf. low-spin t2;). However with the increase of temperature, Ileff gradually increases.
i
62. Both the tig and t2 configurations indicate the presence of two unpaired electrons in each case,
i
but at very low temperature, the tig system records Ileff::::; 0 while the t2 system records a finite
th
value of Ileff'
i
63. Temperature dependence patterns of Ileff for the t 2 and t2~ configurations are different.
e/
64. For the 1st transition series, very often, number of the unpaired electrons can be calculated from
t.m
the Ilobs values but this technique fails for the heavier congeners.
65. For the 1st transition series, Ils is roughly applicable while for the heavier congeners, III is roughly
applicable.
66. For the low-spin octahedral complexes of Mn(III), Os(IV) and Ru(IV) (each system is character-
e
ised by t2;), Ilobs follows the sequence:

er
Ilobs (300 K): Mn(lll) (3.5 B.M.) ) Ru(IV) (2.65 B.M.) ) Os(IV) (1.50 B.M.).
(cf. Ilspin ::::; 2.8 B.M.).
H
• For the heavier congeners, temperature dependence of Ilobs is more pronounced.

67. It is easy to distinguish the oxidation states of 'Mn' from the Ilobs values but it is difficult to
k
determine the oxidation states of the heavier congener 'Re' in the same way.
lic
68. The observed magnetic moment (at room temperature): Ilobs ::::; 1.50 B.M. for an Os-complex
i,
apparently suggests the +3 state (i.e. t 2 Ilspin = 1.73 B.M.). But this prediction is not correct.
C
69. At very low temperature, the t 2; configuration leads to: Ilobs ::::; 0 though there are two unpaired
electrons per metal centre.
70. 2nd order Zeeman effect mayor may not produce TIP depending on the conditions.
71. Like the diamagnetism, paramagnetism arising from the 2nd order Zeeman effect is also field
dependent.
i
72. For the high-spin complexes of iF-system (t 2 ei), Ilobs ::::; Ilspin because of no contribution from the
both spin-orbit coupling and 2nd order Zeeman effect.
73. The small residual paramagnetism in [Co(NH3)6]3+, [Rh(NH 3)6]3+, [Cr04]2-, [Mn04]- etc. can be
explained in terms of 2nd order Zeeman effect (i.e. TIP).
I
74. For [CO(N0 2)6]4-, the plot of XM vs. - produces a straight line with the an intercept, i.e.
T
A
XM = - + B, (A, B are constants).
T
75. XM(2nd order) is only accountable for no unpaired electron or maximum one unpaired electron.
ry
76. Spin orbit coupling contribution to J.leff is relatively more important in the tetrahedral complexes
ra
compared to that in the octahedral complexes.
77. For most of the trivalent lanthanides, XM is mainly due to XM(lst order) but for Sm(lll) and Eu(III),
ib
both XM(lst order) and XM(2nd order) contribute to XM·
• For Sm(lll) and Eu(III), XM(2nd order) is not really temperature independent.
yl
78. For Eu(III), at very low temperature, J.lobs ::::: 0 but at relatively higher temperature J.lobs becomes
m
quite high.
79. The delocalisation factor or orbital reduction factor (k) gives the measure of covalence in the
he
metal-ligand bond.
80. The orbital reduction factor (k) can be estimated from the magnetic data.
81. The orbital reduction factor (k) does not always give a good measure of covalence.
lc
[ NiX 2 {PPh 3 )2 J{x == CI, Br): k == 0.55;
r-:
ea
{[NiCI 4 k == 1.0, [Ni {OH 2 )6 J+:k == 0.93
r-: r+:
th
{[Fe(CN)6 k == 0.80; [Fe{phen)3 k == 1.0

e/
82. Generally, the strong field ligands favour the low-spin complexes but sometimes, the weak field
ligands showing a good nephelauxetic effect can also induce the spin pairing.
t.m
83. Spin state isomerism arises when the difference (~o) in zero-point energies of the two states is
in the order of thermal energy (kBT).
84. Spin state isomerism can be explained in temis of Tanabe-Sugano diagram.
85. Tanabe-Sugano diagram predicts the ease of spin pairing sequence: cf ) d' ) cP. cr )
e
86. (i) Condition for spin state isomerism: 10Dq ::::: P.

er
(1'1·) Con d·'

Itlon .&lor h'Igh ' comp1.& ' 10Dq
- < (10Dq)
H
-spIn ex I ormatIon: - --
B B cross-over Tanabe-Sugano
diagram
k
10Dq (10Dq)
(iii) Condition for low-spin complex formation: -B- > -B-
lic
cross-over
87. Most of the Fe(lll) complexes are the high spin complexes.
C
• Only very few complexes of Fe(lll) are low-spin.

88. Only very strong field ligands like CN- can produce the low-spin complexes with Fe(III).
89. The ease of spin pairing leading to the low-spin complexes runs as:
d 6 ) d 7 ) d 4 ) d 5•
90. The ease of spin pairing can be rationalised in terms of exchange energy.
91. Spin-state isomerism is not expected in the tetrahedral complexes,
92. 10Dq values for [Fe(OH 2)6]3+ and [Fe(dtc)3] are 14,000 cm- l , and 15000 - 18000 cm- l respec-
tively, i.e. 10Dq values are comparable. [Fe(OH 2)6]3+ is a high-spin complex while [Fe(dtc)3]
remains in a temperature dependent equilibrium (involving the spin state isomerism).
93. Generally, the very strong field ligands produce the square planar complexes with Ni(II) but
sometimes, the weak field ligands with the S-donor sites can also form the square planar com-
plexes with Ni(II).
94. The position of the high-spin ~ low-spin equilibrium can be controlled both by temperature
variation and pressure variation.
95. Magnetic moment of [Fe(dtc)3] (dissolved in CHCI 3) decreases with the increase of pressure.
ry
96. The equilibrium constant for the equilibrium l.s. ~ h.s. can be deterimined from the knowledge
ra
of J.lh.s.' J.ll.s and J.lobs·
97. For the spin state isomerism, the spin transition curves (i.e. (Xh.s. vs. temperature) are of different
ib
types depending on the systems.
98. [Fe(phen)2X2] (X = NCS, NCSe) shows the abrupt spin transition curve and at 0 K, it shows only
yl
some residual paramagnetism.
m
• With the increase of temperature, J.lejf of [Fe(phen)2X2] increases sharply.
99. With the increase of temperature, J.leffof [Fe(phen)2X2] (X = NCS, NCSe) increases abruptly while
he
for [Fe(dtc)3]' J.lejf increases slowly and even at high temperature, its J.leff is not saturated.
• Spin transition curves of [Fe(phen)2X2] and [Fe(dtc)3] are of different types.
lc
100. [Fe(dtc)3] shows the spin-state isomerism but [Fe(dtc)2X] (X = Cl, Br, I) does not show the spin-
state isomerism (J.lejf = 3.9 - 4.0 B.M.).
ea
101. [Fe(S2CNH2)3] exists as a high-spin complex (J.lobs ~ 5.80 B.M.) while [Fe(S2CNR2)3] (R = alkyl
group) remains in a thermally controlled spin state equilibrium.
th
102. Fe(III) complexes of ~-diketonates are high-spin while the complexes of monothio-~-diketonates
remain in an equilibrium of spin-state isomerism.
e/
t.m
Fe"i (high-spin) ; Felli (high-spin~ low-spin)

e
er
H
III III
Fe Fe
k
lic
(high-spin~ low-spin) (high-spin) (high-spin)

C
103. Ferriheme proteins experience the spin-state isomerism.

104. Depending on the conditions, the spin-state isomerism may also prevail in the complexes of
Ni(II).
• [NCI 2(detu)4] shows an anomalous magnetic moment.
detu = N, N'-diethylthiourea.
105. [Ni(TAAB)X2]· H 20 (X = Cl, Br) shows the spin state isomerism (J.lejf ~ 1.6 B.M.). TAAB =
tetrakisanhydroaminobenzaldehyde.
• [Ni(TAAB)]X2 (X- = PF6-, BF4-, CI04-): diamagnetic
• [Ni(TAAB)]X2 (X- = 1-, SCN-, N0 3-): J.leff~ 3.2 B.M.
• With X- = Cl-, Br-, the complex forms a stable monohydrate while for X- = l~, it cannot form
the hydrate complex.
• Dehydration of [Ni(TAAB)X2] . H 20 (X- = Cl-, Br-) leads to the elimination of HX instead of
H 20.
• In the above complexes, among the halides, 1- appears as a stronger field ligand than Cl-,
Br-. This is an unusual observation.
ry
106. Spin state isomerism may also occur in the square planar complexes of d 5, d7 and t!' systems.
107. Spin state isomerism may also prevail in the five coordinate complexes (both D 3h and C 4v symme-
ra
try).
108. Mn(II)-phthalocyanine shows an anomalous magnetic moment (Jlobs = 4.5 B.M.).
ib
Hints: Spin state isomerism in the said square planar complex.
yl
109. Depending on the condition, there may be three spin states in the square pyramidal complexes of
~ and cf' systems.
m
• In the square pyramidal complexes of ~ and cf' systems, S = ~ and 1 are the intermediate spin
he
2
states respectively.
110. Spin-admixed ground state may appear in the square pyramidal complexes (C 4v ) of Fe(III).
lc
111. [Fe(dtc)2X] (X = halogen) shows Jlobs ::::: 3.9 - 4.0 B.M. at room temperature.
112. Magnetic property of [FeIII(TPP)X] (TPP =meso-tetraphenylporphyrinate, X- =monodentate anionic
ea
ligand) depends on the nature of X-.
th
• x- = Cl-, S = 2. (h.s.); X- = CIO;, S = spin-admixed state

2
e/
r( = ~) r( S= %)
t.m
• [Felli (CN)z (TPP) S but [Felli (TPP)( OHz)z
113. Magnetic moment of [FeII(TPP)L] depends on the nature of L.

L = strong field ligand (S = 0), L = weak field ligand (S = 2).
e
• [FeII(TPP)] shows the spin state S = 1.

er
114. Magnetic moment of [Fe(NO)(salen)] increases rapidly with the increase of temperature. After
this abrupt change, Jleff gets saturated.
H
Hints: S = ~ (low spin) to S = ~ (intermediate spin), abrupt spin transition at -175 K.

2 2
k
115. Anomalous magnetic moment may arise either due to the mixture of geometrical isomers or due
lic
to the spin state isomerism for a particular geometry. These can be distinguished by considering
the temperature dependence of their magnetic properties.
C
116. Structural isomerism may lead to the anomalous magnetic moments.

117. 'Octahedral ~ square planar' equilibrium is very often found in the Ni(II)-complexes to produce
the anomalous magnetic moments.
118. The Lifschitz salts may remain in two forms depending on the conditions.
diamagnetic (yellow), paramagnetic (blue)
• The yellow Lifschitz salts may be converted into the blue salts on standing but on heating the
blue salts are again converted into the yellow salts.
• ~obs:= 2.6 B.M. for the Lifschitz salts and it can be shown that ~~bs := ~~(octahedraI)'
119. • Yellow coloured [Ni(trien)]2+ becomes blue coloured in the coordinating solvents.
• Bis(salicylaldoximato)nickel(II) is colourless and diamagnetic, but when recrystallised from
a coordinating solvent like pyridine, green coloured paramagnetic crystals are obtained.
• Lifschitz salts show the variable properties (e.g. colour and magnetic properties) depending on
the conditions like nature of the counter anion, solvent, exposure to atmosphere, solvent of
crystallisation, etc.
ry
120. Many Schiff base complexes of Ni(II), i.e. NiL2 show the anomalous magnetic properties.
LH = Schiff base obtained through the 1: 1 condensation of salicylaldehyde and substituted eth-
ra
ylenediamine.
ib
Hints: NiL 2 ~ NiL 2
yl
Octahedral tridentate) (square planar bidentate)
( (O,N,N)L (O,N)L
m
121. [Ni(CI0 4)2(pY)4] may remain in an equilibrium mixture of two geometrical isomers differing in
colour and magnetic properties.
he
R
"
/,c-o
.... _-- lc
122. NiL2 :
"c-o
L-= R ' - C : -
.. _---
ea
R/
th
(i) R = Me, R' = H: [NiL2] (paramagnetic)

(ii) R = Me3C, R' = H: [NiL 2] (diamagnetic)
e/
(iii) R = i-Pr, R' = H: anomalous magnetic property of [NiL 2]

(iv) R = Me, R' = Ph: anomalous magnetic property of [NiL2].
t.m
123. Magnetic moment of bis(N-methylsalicylaldiminato)nickel(II) increases when dissolved in both

the coordinating and noncoordinating solvents.
• If a bulky R-group is present at the ortho-position of the phenolic OH group of the benzene
e
ring, then the magnetic moment does not change on dissolution in a noncoordinating solvent.
er
H
k
lic
C
(i) R' = R = H, J.leff increases on dissolving [NiL 2] in a noncordinating solvent.

(ii) R' =H, R =bulky alkyl group, J.leffof [NiL 2] does not increase on dissolving in a noncordinating
solvent.
(iii) R = H, R' = bulky alkyl group, J.leff of [NiL 2] increases when dissolved in the noncoordinating
solvents.
124. When solid [Co(acac)2] is dissolved in a noncoordinating solvent, J.leff slightly increases.
• In case of [Ni(acac)2]' J.leff" changes remarkably when dissolved in a noncoordinating solvent.
• If Me group is replaced by CMe3 in the skeleton of acac, then J.leff of [Co(acac)2] does not
change when dissolved in a noncoordinating solvent.
125. [NiL2X 2] (L = substituted phosphine ligand, X- = halide) shows an anomalous magnetic moment
in a noncoordinating solvent. Ileff depends on temperature and pressure also.
• Ilobs = 2.7 B.M. It indicates an equilibrium mixture of [NiL2X 2] having the composition.
square planar form: 30%; tetrahedral form: 70%
• Ilobs and colour of [NiL2X 2] depend on the size of the substituents on phosphine and X-.
• Ilobs of [NiL 2X 2] in solution decreases with the increase of pressure.
ry
126. Bis(N-sec-alkylsalicylaldiminato)nickel(II) shows an anomalous magnetic moment when dissolved
ra
in a noncoordinating solvent.
• With the increase of temperature, Ilobs increases but with the increase of pressure Ilobs decreases.
ib
yl
m
he
with the increase of bulkiness of R, magnetic moment of [NiL2] increases.
• The electronic spectra and magnetic moment of [NiL2] depend on the size of R, temperature
lc
and pressure.
ea
• With the increase of temperature, the intensity of peak at 16,000 cm- I decreases while the
intensities of peaks at 7,200 cm- I and 11,200 cm- I increase.
th
e/
t.m
127.
e
R'
er
(i) For X = S, there is an equilibrium:

square planar (low spin) ~ tetrahedral
H
(ii) For X = 0, there is an equilibrium.

square planar (high spin) ~ tetrahedral
k
128. Ilobs of bis(N, N-diethylaminotroponeiminato)nicke(II) (when dissolved in a noncoordinating

lic
solvent) decreases remarkably with the increase of pressure.

129. For Co(II), the 0h ~ Td equilibrium is very often noted.
C
• [Co(acac)2] can lead to the 0h ~ Tdequilibrium giving rise to an anomalous magnetic moment.
• [Co(NCS)2(P-toluidine)2] when dissolved in DMF, Ilobs changes and an intense band at
15,870 cm- I appears with a weak band at 19,800 em-I.
130. [Co(NCS)2(P-totudine)2] when dissolved in DMF, Ilobs decreases from 5.2 B.M. to 4.88 B.M. It
indicates that the complex remains in a 1: 1 mixture of Td and 0h forms.
Hints: Il;ff = aoct.Il~t. + aTet.ll~et.
131. Thermochromism of (NRxH4- x) [NiCI4] (x = 1, 2, 3) can be explained by considering the temperature
dependent 0h ~ Td equilibrium.
132. Magnetic property of bis(N-methylsalicylaldiminato)cobalt(ll) changes when dissolved in a

noncoordinating solvent.
• A similar situation arises for the corresponding Ni(ll) complex.
133. Regular tetrahedral Ni(ll) complexes show the higher Jlejf compared to their distorted complexes.
• Jlejf bears an inverse relationship with the degree of distortion in the tetrahedral complexes of
Ni(II).
ry
134. According to Goodenough-Kanamori-Anderson Rule (i.e. GKA rule), 180 0 superexchange
ra
leads to an antiferromagnetic coupling while 90° superexchange leads to a ferromagnetic ex-
change.
ib
135. In Heisenberg-Dirac-Van Vleck (HDvV) equation for an exchange interaction between two spins
(SI = S2 = ±). the i-value gives a measure of energy gap between the singlet and triplet states,
yl
m
i.e. ~Es = I,D = 12JI
he
136. The orthogonal orbitals lead to a ferromgnetic exchange while the nonorthogonal orbitals lead to
an antiferromagnetic exchange.
137. In an octahedral geometry, eg(M) and PriL) orbitals are nonorthogonal while t 2g (M) and PclL)
lc
orbitals are orthogonal.
ea
138. In an octahedral geometry, t 2g (M) and Pn(L) orbitals are nonorthogonal while eg(M) and Pn(L)
orbitals are orthogonal.
th
139. CaMn03 is antiferromagnetic while the mixed oxide containing Fe(lll) and Cr(III) is ferromagnetic.
140. NiO and MnO crystals are antiferromagnetic.
e/
141. The mixed oxide containing V (II) and Ni(II) is ferromagnetic.

142. NiCl 2 crystal experiences a ferromagnetic exchange while NiO crystal experiences an anti-
t.m
ferromagnetic exchange.
143. NiCl 2 crystal is ferromagnetic while MnCl 2 crystal is antiferromagnetic.
144. Ferromagnetic Cu(ll) complexes are well known but ferromagnetic interaction in VO(IV) or
e
MoO(V) complexes is rarely noted.

er
145. CrCl 3 crystal shows the ferromagnetic property.

146. CuCl 2 and CoCl 2 crystals show the ferromagnetic interaction.
H
147. Mixed oxides of Ni(ll) and Cr(III) show an antiferromagnetic interaction.

148. GKA rules can be explained in terms of 3-centred molecular orbital formation.
k
149. Intramolecular and intermolecular cooperative magnetic exchange interaction can be distinguished
lic
by an isomorphous dilution.
150. K4[Ru2ClIOO] is diamagnetic.
C
151. Magnetic properties of CU2(CH3C02)4· 2H 20 can be explained by considering the 8-bonding.

152. There are evidences to support the fact that the antiferromagnetic coupling in CU2(CH3C02)4· 2H 20
arises from the superexchange interaction.
153. The antiferromagnetic coupling in cupric formate tetrahydrate or [Cu2(HC02)4(NCS)2]2- can be
explained better by considering the superexchange path rather than the 8-bonding path.
154. Temperature dependence of the magnetic property of [Cu(CH3C0 2)2(OH 2)]2 indicates that the
energy separation between the ground singlet state and excited triplet state is not very high.
155. The magnetic property of the dihydroxidobridged dinuclear complexes of the following skeleton
depends on the LCu-O-Cu angle.
2+
'"
N N = didentate chelating ligand.
ry
• For the bridge angle Leu-O-Cu = 90°, the accidental orthogonality leads to a ferromagnetic
ra
exchange.
• For the bridge angle LCu-O-Cu ) 97.5°, the dinuclear complex experiences an antiferro-
ib
magnetic exchange.
yl
m
156.
he
lc
The above type dihydroxido-bridged dinuclear complexes of Cr(III) experience a ferromagnetic
exchange for the bridge angle close to 90° while the system experiences an antiferromagnetic
ea
exchange for the higher bridge angle.
• Compared to the analogous Cu(II) complexes, in the Cr(III)-complexes, the superexchange
th
interaction is relatively weaker (measured by the i-values).

157. Doubly oxido-bridged dimers of oxidomolybdenum(V) attain the antiferromagnetic exchange
e/
through the direct metal-metal bonding while the antiferromagnetic exchange in the singly
oxido-bridged dimers of oxidomolybdenum(V) is attained through the superexchange process.
t.m
0 0 0
o 0
•
11/ 11/
-Mo-O-Mo-
11/
-Mo-O-Mo-
1/ 11/°,,- 11/
e
/1 /1 /1 /11o -Mo
"-0/
Mo-
er
/ 1 I
\_------ -------) V
'V
H
Antiferromagnetic interaction
Antiferromagnetic interaction through superexchange through direct metal-metal bond.
k
• [M0203(S2CEt)4] is diamagnetic.
lic
158. Tridentate Schiff base complexes of VO(IV) show the subnormal magnetic moments.
• The corresponding Cu(II) complexes may also show the subnormal magnetic moment but the
C
mechanism is different from that occurring in the corresponding VO(IV) complexes.

159. The antiferromagnetic interaction in the doubly oxido-bridged dimers of oxidomolybdenum(V) is
stronger than that prevailing in the analogous dimers of oxidovanadium(IV).
o
>
0 0 0
• Jleff of
L,,-~/O,,-~/L~eff0f L~f°,,-~(L
L/I"-o/I"-L
L L.
L/I"-o/I"-L L L
160. M0 20l+ (aq) is diamagnetic with a Mo-Mo single bond.

161. Homometallic dimers having the CU202 ring in the Cull-complex, the (MOO)202 ring in the
MoO(V)-complex, the (VO)202 ring in the VO(IV)-complex are antiferromagnetic while the
heterometallic dimers having the CU(VO)02 ring or CullCrllI02 ring are ferromagnetic.
• Fo~ the bridge angle of 90°, accidental orthogonality (causing ferromagnetism) arises in the
CU202 ring while strict orthogonality (causing ferromagnetism) arises in the CU(VO)02 ring.
ry
162. The iron-sulfur protein, Fe2S2(S--cYS)4, i.e. 2Fe-2S ferredoxin shows a subnormal magnetic moment
in the reduced form while the protein is diamagnetic in the oxidised form.
ra
163. The antiferromagnetic coupling in the single oxido-bridged dinuclear complex of Cr(III) is better
than that in the corresponding hydroxido-bridged dinuclear complex.
ib
• 21 = -180 cm- 1 for [(H3N)sCr-0-Cr(NH3)s]Br4
while 21 = -15 cm- 1 for [(H 3N)sCr-OH-Cr(NH 3)s]Brs.
yl
164. [Cr(CH 3C0 2)2· H 20]2 is diamagnetic.
m
165. [Mn2(CO)IO] is diamagnetic
166. Re2CI§-, Re3X9 (X = halogen) clusters are diamagnetic.
he
167. The oxido-bridged dimers [M 20X IO]4- (X = CI, Br; M = Ru or· Os) are diamagnetic.
168. Ferrites show the ferrimagnetism.
lc
169. Canting of spins very often leads to a weak ferromagnetism.
170. Canted ferromagnetism exists in (NBu4)[CuCr(OX)3] (magnetic moment corresponds to 3-unpaired
ea
electrons).
171: CsCoCI 3· 2H 20 shows the canted antiferromagnetism.
th
172. Triangular and terahedral arrangement of spins favouring the antiferromagnetic interactions may
lead to the situation of spin frustration.
e/
173. Competing spin interaction exists in [M 30(acetate)6(OH2)3]CI· 5H 20.

174. Competing spin interaction exists in the tetranuclear system, [Fe402(acetate)7(bpY)2]+.
t.m
175. Bleany-Bowers equation may be obtained from the van-Vleck equation.

176. Bleany-Bowers equation can explain the magnetic properties of the binuclear complexes of Cu(II).
177. Kotani expression can explain the temperature dependence of Jleff for the ground T-term.
e
178. Triangular trinuclear complexes of Cu(II) (i.e. Cull-centres are placed at the corners of an equi-
lateral triangle) shows Jleff = 1.0 B.M.
er
179. Bleany-Bowers equation of XM for the dimeric forms of Cu(II)-acetate can lead to the Curie-Weiss
H
equation.
k
lic
C
APPENDIX VIII: DERIVATIONS OF SOME IMPORTANT RELATIONS OF

MAGNETOCHEMISTRY
(A) Magnetic Moment when MultipletWidth Large Compared to ksT(i.e. Thermal Energy)
For the condition tillJ. J+l ) kBT, the spin-orbit coupling constant (A) is high (ef t:£J. J+l = A(J + 1), Lande
Interval Rule) and the Land S vectors interact strongly to produce the resultant vector J. The corre-
ry
sponding J becomes a good quantum number. Under the present condition, the lowest level is only
ra
populated and the quantum number J (not the Land S quantum numbers) determines the magnetic
moment. The directions of the resultant momentum and resultant magnetic moment are opposite to each
ib
other. The coupling of Land S vectors and the resulting magnetic moments are shown in Fig. A.l. The
spin magnetic moment (J..Ls) vector is taken as the double of spin momentum vector while the orbital
yl
magnetic moment (JJ.L) vector is taken as the orbital momentum vector (cf y/y, = 2, Y stands for the
gyromagnetie ratio, Sec. 8.9).
m
he
S sin a = L sin 8
4 •
S
lc a S cos a
= J - L cos 8
ea
a
(~= 8 + a)
th
L
e/
a:>
en
o L cos 8
c.>
...J
t.m
= J - S cos a
8
~s
e
L sin 8 = S sin a
er
(a) (b)
H
Fig. A.I (a) Coupling of the Land S vectors to give the resultant J vector. (b) Components of Land S along J in terms
of triangle of vector addition.
k
The Land S vectors precess rapidly about the direction of the resultant J vector. Consequently, J.lL
lic
and J.ls also precess rapidly about the J-vector. Effectively, J.lLS (resultant magnetic moment) denoted by
AB precesses rapidly about the J-vector. Thus in any finite time, the vector CB averages out to zero and
C
J.lJ (denoted by AC) is effectively given by J.lLS'

We can write:
J2 = L 2 + S2 + 2LS cos<t> = L 2 + S2 + 2LS cos (L, S), (Fig. A.la, <t> = a + 8)
L2 = (J - S cosa)2 + (S sina)2
= J2 + S2 cos 2a - 2JS cosa + S2 sin 2a
(Fig. A.lb)
= J2 + S2 (sin2a + cos 2a) - 2 JS cosa
= J2 + S2 - 2 JS cos a = J2 + S2 - 2JS cos (S, J)
i.e. S cos (S, J) = (J2 + S2 - L 2)/(2J)

S2 = (L Sine)2 + (J - L cose)2 }
= L 2 sin 2e + J2 + L 2 cos 2e - 2JL cose (Fig. A.I b)
= J2 + L 2 - 2JL cose = J2+ L2 - 2JL cos (L, J)
i.e. S2 = J2 + L2 - 2JL cos (L, J).
ry
III (i.e. AC) = mOlnent due to L in the direction of J + 2 x moment due to S in the direction of J
ra
= BLcos(L, J) + 2BScos(S, J)
B(J 2 +L2 _S2) 2B(J 2 +S2 _L2 )
ib
= +------
2J 2J
yl
2
= ~(3J2 + S2 _ L2) = ~J(3J2 + S2 - L )
m
2J 2J2
2 2 2
he
2J +J2 +S2 _L ) ( J2 +S2 _L )
=BJ ( =BJ 1 + - - -
2J2 2J 2
=gBJ lc
ea
J2+S2_ L2
where g=I+----
2J2
th
Using, · S=JS(S+I)~,L=JL(L+l)~ andJ=JJ(J+l)~,

2n 2n 2n
e/
We get:
t.m
. -I J(J+I)+S(S+I)-L(L+I)
gJ l.e.g- + ()
2J J + 1
e
h
Expressing J in the unit of - , we can write:
2n
er
III = gB)J(J + I) i.e. IlJ = gJBJJ(J + 1)

H
• When S = 0, J = Land g = 1, IlJ = ilL = JL(L + I) B

k
andg=2~flJ =Ils =2JS(S+1)B=J4S(S+I)B

lic
• When L=O,J=S
Jn (n + 2) B. (S = !!.-,2 n = number of unpaired electrons)

C
(B) Magnetic Moment when Multiplet Width Small Compared to ksT{i.e.Thermal Energy)
Under the condition, ~E1, 1+1 ( kBT, all the J-Ievels may be assumed to be populated. This happens when
the spin-orbit coupling constant is small i.e the vectors Land S do not effectively couple. By considering
Fig. A.I a, we can write:
IlCs= ilL + Il§ + 2J.lLJ.lSCOSq> = J.lC + J.l§ + 2J.lL· J.ls; (cf scalar or dot product of two vectors)
i.e. AB = 11 = (L2 + 4S 2 + 4L· S)~2; (J.ls is twice the spin Inomentum vector)
2 2
\\I'here L· S = LS cos <t> = LS cos (L, S)

J2 = L 2 + S2 + 2LS cos <t> = L 2 + S2 + 2LS cos (L, S)
J2_ L 2_S2 1 (1 + I) - L (L + I) - S(S + I)
i.e. LScos(L, S) =- - - -
2 2
ry
Expressing the vectors J, Land S in the - unit.
21t
ra
( Cf. J = ~J(J + 1)~, L = ~L(L + 1)~, S = ~S(S + 1)~)
ib
21t 21t 21t
The Land S vectors are at different angles and the resultant vector J becomes different for the
yl
different orientations of the Land S vectors. However, for all such orientations, the Land S vectors are
m
the same. Each l-level can have (21 + I) orientations (cf M J can vary from +1 to -1).
he
The statistical average of L· S, i.e. L· S for all possible orientations is proportional to the following
sum which reduces to zero.
IL+sl
L
lc
(21 + 1)[1(1 + I) - L(L + I) - S(S + I)] = 0
ea
J=IL-si
(21 + I) denotes the multiplicity of a particular 1 level. (21 + I) arises from M J = +1 to -1.
th
It is illustrated for L = S = I, i.e. 1 = 2, I, 0

sum = 5 x (6 - 2 - 2) + 3 x (2 - 2 - 2) + I x (0 - 2 - 2) = 10 - 6- 4 =0
e/
It leads to:
t.m
Jl2 = (L2 + 4S2 + 4L· S )~2 = (L2 + 4S2)~2
Expressing the Land S vectors in the unit of 2: (C/. L = ~L (L + 1) 2h1[ , S = Js(S + 1) 2h1[) , we
e
er
can write:
Jl = ~[L(L + 1) + 4S(S + I)] ~

H
The above expression can be obtained by considering the inefficient coupling between the Land S
k
vectors. Under this condition, the resultant magnetic moment arises from the sum total of the spin and
lic
orbital effect, i.e.

N N N ~2
C
2 2
XM =X L +X S =~+~=_A
3k BT 3k BT
-[L(L+I)+4S(S+I)]
3k BT
i.e.
(C) Magnetic Moment when Multiplet Width Comparable to k s T (Thermal Energy)

Under the condition, different l-levels will be polulated thermally according to Boltzmann distribution
law and each l-level will contribute to XM according to their Boltzmann population densities. This
aspect has been already discussed and illustrated in Sec. 8.14.
Note: In deriving all the above expressions, the temperature independent paramagnetism (TIP),
i. e. 2nd order Zeeman effect to contribute to the paramagnetism has been ignored.
(0) Curie Equation

Curie equation gives the relationship between the molar magnetic susceptibility (XM) and the magnetic
moment (J.!) and temperature.
ry
In presence of an external magnetic field, each I-level splits into (21 + 1) components (M] values: +1
ra
to -1). (cf Fig. 8.14.2). When a paramagnetic molecule interacts with the external field (H), its energy
is lowered by fiH where fi is the projection of the magnetic moment (J.!) along the direction of H. It
ib
leads to:
yl
_ dE
fl=--
dH
m
i. e. fi oc decrease of energy of the molecule with the increase of the applied magnetic field.
he
This decrease in energy occurs due to the alignment of the magnetic dipole in the direction of the
field.
XM is given by: lc
ea
NA . . . NA -
'X M = H x (average magnetIc moment component along the dIrectIon field H per molecule) = fi. x Jl av
th
- LniiI i LniiI i
where Jl av =-~--=--
e/
£..Jni NA
The population density of the levels is thermally controlled by Boltzmann's law, i.e.
t.m
ni = noexp[-~/(kBT)]
where ni and no denote the number of molecules in the i-th level and reference level respectively and ~i
is the energy difference between these two levels.
e
g~J I (I + 1). On application

er
Let us assume that the magnetic moment (J.!) of the substance is given by
of the field, the I-level splits (1st order Zeeman effect) into (21 + 1) components denoted by the M]
H
values (ranging from -I to + 1). Energy of a particular level is given by (cf Fig. 8.14.2) M]g~H.
~Mj =E Mj -EMj=o =M]g~H-Oxg~H=M]g~H
k
Thus the energy difference between the successive levels (i.e. 11M] = 1) is g~H which is about
lic
1 cm- 1 for H = 10,000 gauss. It indicates that gr3H is quite small compared to kBT (::::: 200 cm- 1 at
C
300 K).
~ = projection of Jl along the field =- dE =- M J g~

dH
ry
It is reasonable to assume MJ g~H «I and this leads to:
ra
kBT
ib
exp ( M1 g~H J'" I - MkBTg~H, (cf. exp(x) '" I + x, for very small values of x).
J
yl
kBT
m
he
= [1 + Jg~H] +[1 + (J -1)g~H] +... +[1 +0] + ... +[1- (J -1)g~H]+[I_ Jg~H]
kBT kBT
lc kBT kBT
ea
=(2J + 1)
th
I. (-MJg~)exp( Mlg~HJ= I. (-MJg~)(I- Mlg~HJ

e/
MJ=-l kBT MJ=-l kBT
J[
t.m
Jg~H] + [ (J-l)g~ 1+ (J -1)g~H] +

=[Jg~ J[ 1+-- +Ox(I-0)+ .
kBT kBT
+[ -(J -1)g~J[I- J(J -1)g~H]+[-Jg~J[I_Jg~H]

e
kBT kBT
er
H
k
lic
C
= 2g2~2H[ J 2 +(J-l) 2 + +0
]
kBT
2g2~2H [J(J+l)(2J+l)] 2 2 2 2 n(n+l)(2n+l)
= x X; c/.l +2 +3 + +n = - - - - -
kBT 6 6
2A2
=~[J(J+1)(21 + I)J
3k BT
Thus it gives:
_ g2~2HX[J(J+l)(2J+l)J g2~2H [( )]
J.l = =--xJJ+l
av 3k B T x [(2J + 1)] 3k B T
Now XM can be expressed as follows:
ry
ra
J.l = g~~J(J + 1) i.e. J.lJ = gJ~~J(J + 1)
ib
It gives:
Abridged (i.e. cut-short) derivation of Curie equation: Because of the thermal agitation, all the
yl
paramagnetic molecules with the magnetic moment Il cannot be oriented towards the field (H) direc-
m
tion. There will be a random distribution of the paramagnetic molecules in terms of their orientations
with respect to the field direction. In other words, they will be oriented at different angles (say, 8 b 8 2,
he
8 3, •.•. ) with the field direction. Because of this random orientation, the observed average moment will
be less than the real moment J.!. If a paramagnetic molecule (with Il moment) is oriented at an angle 8
lc
with the field direction, then effectively it makes the contribution J.!cos 8 (=
Thus, XM can be expressed in terms of iIavas follows:
iI) along the field direction.
ea
X - NAiIav
H
th
M-
If a fraction of the molecules is oriented at an angle 8 with the direction of field, then contribution
e/
of this fraction (f =!!i-, say] to iI av is given by:

t.m
e no
= (J.! cos 8) x fraction of the molecules at an angle 8

J.!e
iIav = average J.!e's over all the possible values of 8.
e
In presence of the field (H), there will be a decrease in the energy of the magnetic dipoles:
er
~=-iIH
H
It indicates that energy of the paramagnetic molecules in presence of a field (H) depends on their
k
angle (8) of orientation. According to the Boltzman distribution law, ni = no exp (- I1E ] where ni and
kBT
lic
no refer to the population of the i-th level and O-th level (say ground or reference level) and I1E gives
the difference in energy between these two levels. It leads to:
C
n·
f e = ---l...- = fraction of the molecules at an angle 8, i. e. fraction of the molecules at the i-th
no
= JlCOse[1 + JlH cose];

kBT
assuming Il
H
cose
kBT
«I and exp(x) '" I + x
Jl2 H cos 2 e when x is very small; cf JlH cos e ::: few cm- I
= Jlcose+----
kBT andkBT ::::: 200cm- 1 at 300 K
ry
iIav is the average of Jle's over all the possible values of 8. It gives.
ra
-- H 1 H 2 2
= Jlcose + Jl2 H cos 2 e/(kBT) = 0 + - x ~
ib
iI av = _Jl_
3 kBT 3k BT
yl
1
(Note: The statistical average of cos e over a sphere is zero while that of cos 2e is "3 . It is proved in
m
any standard textbook on Physical Chemistry.)
he
- N 2
_ NAJlav -~
'XM - H - 3k T lc
B
ea
(E) Derivation of van-Vleck Equation
Energy of the i-th level with respect to that of a reference level in presence of an applied magnetic field
th
(H) is given by:

= EP + E}H + EPW +....
e/
E;
Here, E[ =energy of the i-th level in absence of the magnetic field; E~ and EP are the first-order and
t.m
second order Zeeman coefficients.

In presence of a magnetic field, energy of a paramagnetic molecule decreases as follows:
f1i = - dEi = -E{ - 2HEF ; (Neglecting the higher term).

e
dH
er
We have:
H
NA - - I,n;iI;
'XM = - x Jl av and Jl av = - -
H I,n;
k
The population density at a particular level is controlled by the Boltzmann's distribution law.
lic
n; = no exp[ -E;/(kBT)]
C
where n; and no denote the number of molecules in the i-th level and reference level respectively and E i
gives the energy difference between these two levels.
Splitting of the energy levels by the first order Zeeman effect gives the energy difference (=gpH)
between the successive levels (i.e. 11MJ = 1 ) (cf Fig. 8.14.2). This energy difference (ca. 1 cm- I for
H = 10,000 gauss) is quite small compared to kBT::::: 200 cm- I at 300 K, i.e. gpH/(kB1) « 1.
The second order Zeeman effect is still less. For the small values of x, exp(x) becomes approximately
(1 + x). Thus under the present conditions:
ry
E~ J}( 1- E!k~TH J( 1- E!/~BTH J'" {exp (- k:T
E~ J}( 1- E!k~TH J
2
ra
exp ( - kB~ '" exp - k:T
E.) { (
ib
yl
m
he
(using the expression of iIi ).
N-
lc
= ~av
ea
From the relationship, XM and properties of XM, which is independent of the applied
magnetic field (H), we can conclude:

th
(i) in the experession of iI av ' there cannot be any term of an order higher than H in the numerator
e/
and the terms in the denominator must be devoid of H;

t.m
it leads to: (1 - E{kBTH J:: : 1 in the denominator

(ii) in absence of the field (i.e. H =0), iIav must be zero; thus the numerator of the expression of iIav
e
must be zero for H = 0; it leads to:

er
E? J= o.
Li -E{ exp (- kBT
H
Thus we can write:

k
~[
lic
N £..J -E·I + (E{tH -2E.II H

2
+ 2H E{IE{] exp (E?
-- J
NAil A. 1 kBT 1 kBT kBT
X - __t"'_a_v -
C
__, ~--------------=------
M - H - HLexp(-_E? J
i kBT
ry
ra
( E! ) 2 EO
N I, 2E!/ ] ex __i_
_1_ -
ib
A [ k TIP k T 2HE!/ E!
B ( B) ; I ':0= 0 ;(cf. XM is independent of H)
E~)
yl
kBT
I,exp __
(1_
kBT
m
This is the common form of the Van-Vleck equation. Use of this equation to calculate XM requires
he
the estimation of the coefficients, E;o, E/ and E/ I • These can be evaluated quantum mechanically but
these are not discussed here. Depending on the conditions, the above equation may be simplified.
lc
Case I (!lE), }+1 ) knT): The term E? can be taken as zero, i.e. energy of the i-th level in absence of
ea
the magnetic field is taken as zero, i. e. E;o may be considered as the reference energy. Thus the term
exp (- E? ) in the numerator is taken as unity but in the denominator, summation of the exponential
th
kBT
term is replaced by the multiplicity of the J-Ievel, i.e. summation of the levels. It reduces the Van-Vleck
e/
equation as follows:
t.m
e
er
Ignoring the 2nd order Zeeman effect (i.e. E/I ::=; 0), for the large multiplet width compared to knT,
the first order Zeeman effect leads to:
H
E/H = Mjgj~H.
Under this situation, the Van-Vleck equation reduces as follows:
k
lic
C
N AgJt-'
2A2 )( I 2 2 2 2 2
= - - ) [1 +(J -1) + +0 + +(J -1) +1 ]
( kBT 2J + 1
N Agjt-'
2A2 )( 1 2 2 2
= - - ) X2X[1 +(J -1) + +0 ]
(
kBT 2J + 1
ry
~J = gJ~~J(J + 1)
ra
It gives:
Case-II (till), }+1 (kBT): When the multiplet width is small compared to kBT, instead of J, the Land
ib
S vectors determine the magnetic properties. The first order Zeeman effect leads to:
yl
E/H = (ML + 2Ms)~H; MLranges from -L to +L; Ms ranges from -5 to +5.
m
E~ J
In the numerator of Van-Vleck equation, exp __1_ = 1 but in the denominator, the summation of
( kBT
he
the exponential term gives the multiplicity of the level concerned. Ignoring the 2nd order Zeeman
effect, the above conditions lead to: lc
ea
th
e/
t.m
e
er
H
~ (£:)2
k
N
lic
AL., k T
i.e.
C
= N A p2 [L(L+l)(2L+l) + 4S(S+I)(2S+1)]
kBT 3(2L + 1) 3(25 + 1)
It gives: Jl =) L (L + 1) + 4S (S + 1) ~
( ~
+L
ML=O, ~
+L ()()
Mi=L L+l 2L+l; ~
+L
exp
( 0
-~
JI,= ~
+L
1=2L+l
M L --L M L --L 3 M L -+L kBT M L --L
ry
i.e. multiplicity of the level)
ra
ib
yl
m
Note: (ef van-Vleck equation)
he
lc
ea
th
Taking, E[ (= energy of the i-th level in absence of the field H) as zero, (i.e. reference energy), the
e/
term exp (- E? J in the numerator of the van-Vleck equation becomes unity. But summation of the
(E~ Jgives the multiplicity (i.e. degeneracy) of the level concerned [e.g.
t.m
kBT
exponential term, I,exp __1_
i kBT
(21 + 1) for 1; (2L + 1) for L; 2S + 1 for S.
e
er
(F) Magnetic Properties of the Binuclear and TriangularTrinuclear Complexes:

Bleaney-Bowers Equation
H
(a) Energy levels due to the interaction between two spin vectors: Let us consider two spin vector
(say SI and S2) interacting at an angle 8 to generate the resultant spin vector S. Then we can write (ef
k
Secs. A, B):
lic
S2 = S? + Sf + 2S 1S 2 cos8 = S? + S1 + 2S,S2 cos (SJ, S2)

= Sf + Sf + 2S 1 • S2; (ef dot product of two vectors)
C
i.e. 1[
SI· S 2 =- S 2 -S}2 -S22J
2
The exchange interaction energy (E) is given by:
E = -21 SI • S2 = -J[S2 - Sf - SiJ
Here 1 (not quantum number) denotes the exchange coupling constant. 1 is negative for the
antiferromagnetic exchange and 1 is positive for the ferromagnetic exchange. Using the relationship,
S= Js (S + 1) ~
2n
and expressing the spin vectors in the
h
2 unit, we can write:
n
E = -J[S(S + 1) - SI(Sl + 1) - S2(S2 + 1)]

For Sl = S2 = S' (say), we can write:
E = -J[S(S + 1) - 2S'(S' + 1)]
If 8 1 and 8 2 antiferromagnetically couple, then ground state is singlet (i.e. S = 0). Let us determine
the energy difference between the ground state (i.e. S = 0) and an excited state (say S = S).
M: = E s - E S = 0 =- J[S(S + 1) - 2S'(S' + 1)] - J[ 0 - 2S'(S' + I)] =- J[ S(S + 1)]
ry
Thus - J[S(S + 1)] gives the energy of the S-Ievel with respect to that of the ground level (S = 0).
It is illustrated in Fig. F. 1
ra
Relative Energy Spin Multiplicity
8=3 -12J
ib
7
8=2 -6J 5
yl
8=1 -2J 3
8=0 o
m
Fig. F.! Energies and multiplicities of different spin states in a binuclear complex due to the exchange interaction
o.
he
(J = exchange coupling constant). Energy of the ground state is taken as
(b) Bleany-Bowers equation for the binuclear complexes of d 1 or d 9 systems: For the d l and d 9
systems, S 1 = S2 =S' =! , i.e.

lc
the binuclear complex gives the resultant S = 0 (singlet) and 1 (triplet).
ea
2
E s = -J[S(S + 1) - 2S'(S' + 1)]
th
i.e. E _ =-J[0-2X!(!+I)]=-JX-'i='i J
2 2 2 2
e/
5-0
(cj. Fig. 8.31.1.4)
=-J [ lX2-2X~( ~+1)] =-J ( ) =-~J
t.m
ES=I 2-%
MI,O = ES=I - Es=o =%J - (-~J ) = 2J

e
er
For S = 0, multiplicity = 2 x 0 + 1 = 1; for S = 1, multiplicity = 2 x 1 + 1 = 3. Asuming the population

density (controlled by Boltzmann distribution law) at both the S = 0 and S = 1 levels, we can follow the
H
similar treatment used to calculate XM for M:j , j+l ::::: kBT (cf Sec. 8.14) as in the cases of Sm(III), and
Eu(III).
k
lic
2 Lg;J(J +1)(2J +1)exp (- M:J )

NA~ j kBT
C
For, M: j , j+l ::::: kBT, XM = 3k T x ( M: )

B L(2J+l)exp _ _J
J kBT
It is a special form of van-Vleck equation. M:j gives the energy difference between the I-level and
ground J-Ievel, i.e.M:j = Ej - Ej (ground level)
The above equation can be applied with some modifications as indicated below for the binuclear
systems where the spins are mutually interacting.
(i) The term J (= quantum number) of the above equation is to be replaced by S (= resultant quantum
number).
(ii) The term (21 + 1) representing the multiplicity of a particular J-Ievel is to be replaced by (2S + 1)
representing the multiplicity of as-level.
(iii) tiE] (= energy of the J-Ievel with respect to that of the ground J-Ievel, i.e. energy difference
between the J-Ievel and ground J-Ievel) is to be replaced by tiEs, 0 (= energy difference between
the S-level and ground S-level for which S = 0).
Thus the above equation reduces to:
ry
ra
ib
yl
m
1
For the binuclear complexes of d 1 and JJ configurations, S1 = S2 = S' = 2"' ~Eo, 0 = 0, ~ 1, 0 =- 2J.
he
By using these values in the above equation we get:
N g2~2
lc
OX(0+1)(0+1)exP (0)+lX2X3xexp ( 2J
kBT
J
ea
X - A X
M - 3k B T (0+1)exp(0)+3exp ( - 2J J
th
kBT
e/
t.m
e
SJ).
er
2
(Obtained by multiplying the numerator and the denominator by exp ( - k
H
k
lic
C
2 2[ 2 1
= 2N A g ~ 1
1 + -exp (2J
--- J]-1 ~ -1 [ 1+ -exp
1 2J- J]-1 ; N ~ ~ -and
(-- _A_ taking g ~ 2.0
3k BT 3 kBT T 3 KBT 3k B 8
It indicates that XM~ 0 when T ~ 00 (infinity) and XM becomes small for the small values of T. XM
becomes maximum (at the TN temperature) when dlnxAldT becomes zero. It gives:
1211 8.
--::::; - I.e. TN =-51211
- ; TN actually denotes the Neel temperature.
kBTN 5 8k B
• When 1211 « kBT, we can write:
ry
ra
ib
=~[ T]=i[
B
]=i[_I] 8=
yl
3k 1 -21
T 4k T-21 B 4 T- 21 4 T+8' 4k B ·
m
4k B
The above relation represents the Curie-Weiss equation and e is called the Weiss constant.
he
Thus for the binuclear complexes of Cu(II), Ti(III), V(IV), Mo(V), we can write (taking the CU!I
system as a representative example):
[1
_ 2N Ag2~2 + !ex (_~J]-l
lc
ea
_
XM - XM (Cu 2 ) - 3k T 3 P kBT
B
For per metal centre (i.e. per gram atom), it becomes:
th
_! Ag2~2
_XM(cu) -_ N3k [1 + !ex (_~J]-l
e/
Xa - 2 X M(Cu 2 ) - T 3 P kBT
B
t.m
Taking into the consideration of TIP per gram atom, we can write:
XM(cu) = N Aip2 [1+!exp(-~J]-1 +NACl

3k BT 3 kBT
e
er
= 3D [_1_] + NACl, D= N Aip2 ; y=exp(-~J

T 3 + y2 3k B kBT
H
The above equatio~ is described as the Bleany-Bowers equation.

Note: In deriving the above equation of XM, ground level was considered to be S =o. In original Van-
k
lic
Vleck equation, the energy term E[ indicates the energy of the i-th level (in absence of an external
magnetic field) with reference to a level for which the energy is zero. In the present system, energy for
C
the level S = 0 is not zero. The energy values are: £s=o = %J, £S=I = -~J; J is negative for an
antiferromagntic interaction. Thus by using the following form of Van-Vleck equation, XM can also be
expressed to attain the same Bleany-Bowers equation.
LS(S+I)(2S+1)exp (-
2 2 E? )
NAg ~ s kBT (. . )
XM(C U 2 ) = 3k T x (EO ) ,lgnonng TIP
B L(2S+1)exp _ _ i
kBT
ry
ra
exp(-~J+3exp(_1 J
ib
2k B T 2k B T
yl
Multiplying both the numerator and the denominator by exp (-_1_J and rearranging, we get:
m
2k BT
he
lc
ea
X _ 2N Ag2~2 [ I+-exp
1 (2J
--- J]-1
th
M(Cu 2 ) - 3k BT 3 kBT
i.e. the same result is obtained from the both approaches.
e/
(c) Bleany-Bowers equation for the binuclear complexes involving the d 3 system, e.g. Cr!II: Let
t.m
us illustrate the Bleany-Bowers equation for the binuclear complexes of the d3 system, e.g. Cr!II core.
I 3
S = SI = S2 ="2 i.e. S = 0, 1,2,3, i.e. IS] + S2 1 to lSI - S2 1
e
~o,o = 0; ~],O = -21; ~2,O = -61; ~O,3 = -121.

er
XM = N;:B X(~)=(A)X(~)
2 2
:
H
P =0 x (0 + I) x (0 + l)exp(O) + 1 x 2 x 3 x exp(l!-)
k
kBT
lic
+ 2 x 3 x 5 x exp ( 61
kBT
J+ 3 x 4 x 7 x exp ( kBT
12J J
C
Q=(0+I)exP (0)+3xexp ( 21 J+sxexp ( 6J J+7xexp (121J

kBT kBT kBT
_A [6ex P (2x) + 30exp(6x) + 84exp(12x) ] _ J
XM - X ( x---
1+3exp(2x)+Sexp(6x)+7exp 12x) , kBT
=2AX[ 3exp(-10x)+ ISexp(-6x)+ 42exp(0) ]
exp(-12x) + 3exp(-10x) + Sexp(-6x) + 7 exp (0)
(obtained by multiplying both numerator and denominator by exp(-12x), i.e. exp (- 12J
kBT
J)
. -6A[ 14+5exp(-6x)+exp(-lOx) ]
I.e. XM - 7 + 5exp(-6x) +3exp(-10x) +exp(-12x)
ry
1 .
= "2 XM ; PuttIng
ra
Magnetic susceptibility per gram atom in the binuclear complex is given by: Xa
(J J .
D = N Ag2~2 and exp - - - ,l.e. exp(-x) . leads to:
ib
= y, the above equatIon
3k B kBT
yl
14+5 y 6+ y l0 ]
=-3D[ .
m
Xa 6 10 12 + N AU; (TIP has been Included)
T 7+5y +3y +y
he
Xa for different binuclear complexes are given below.
Xa =3D- [ - -12] +NAu for SI = S2 =-

1 e.g. .
TI III II IV V
2 ,Cu 2 , V2 ,Mo 2 , etc. lc
T 3+y 2
ea
4
Xa = 3D[ 5+1 6]+N A U for SI =S2 =1
th
T 5+3y +y
e/
3D[ 14+ 5y 6 + yl0 ] 3 III

Xa = - 6 10 12 + N AU for SI = S2 = -, e.g. Cr2
T 7+5y +3y +y 2
t.m
3D[ 30+14y8+5yI4+yI8 ] . . II
Xa =- 8 14 18 20 + N AU for SI = S2 = 2, e.g. hIgh spIn Cr2
T 9+7y +5y +3y +Y
e
er
_ 3D [ 55 + 30yl0 + 14y18 + 5y24 + y28 ] 5. . III

Xa - -T 10 18 24 28 30 + N AU for SI = S2 =-, e.g. hIgh spIn Fe 2 .
11+9y +7y +5y +3y +y 2
H
In the same way by unsing the van-Vleck equation, Xa for the polynuclear systems (e.g. trinuclear
complex, tetranuclear complex, etc.) can be evaluated. It will be illustrated for the triangular trinuclear
k
complexes.
lic
It may be noted that if we neglect the contribution of 2nd order Zeeman effect (Le. NAu) and assume
that the cooperative interaction is absent (J = 0, L e. y = exp[-J/(kBD] = 1), then the above expressions
C
will lead to the spin-only magnetic susceptibility values. It is illustrated for the d 1 system, S = .!. :
2
N
=_A_ [ J3~J2 =_A_
N [ ~4S(S+1)~J2 =_A_
N [ ~n(n+2)~J2 ;S=-,n=l
1
3k BT 3k BT 3k BT 2
i.e. ~ = ~s = JI (1 + 2)~ = 1.73~

Similary, for the tP-system (i.e. 5 = 1), it leads to: ~ =~ s = J2 (2 + 2)~ = 2.83~ (taking g = 2 and
y = 1)
(d) Bleany-Bowers equation for the triangular trinuclear complexes: Repreasentative examples
ry
3
are: [Cr30(acetate)6(OH2)3]+, [Fe30(acetate)6(OH2)3]+. For the CrlII-system, 51 = 52 = 53 = -. The
2
ra
resultant 5-values may be obtained as follows:
ib
Combination of the 8 1 and 8 2 vectors can give the resultant values 0, 1,2,3 (i.e. l +l to l_l values).
2 2 2 2
yl
These values will vectorially combine with 8 3-
m
° 3 135 1357
and 8 3 ==> -; 1 and 8 3 ==> -, -, -; 2 and 8 3 ==> -, -, -, -.
2 222 2222
he
3 5 7 9
3 and 8 ==> - - - and -
3 2'2'2 2 lc
ea
. d·Icates: 5 =-1 . =-3 ~.tImes; 5 =-5 appears theertImes;
' 5 =-7 appears
It In appears tWIce; 5 appears lour
2 2 2 2
th
.9
tWIce; 5 =- appears on1yonce.
2
e/
1 3 5 7 9
s= - - -
t.m
2 2 2 2 2
Multiplicity = 2 x (2 xi + l) 4(2X%+l) 3X(2X%+l) 2X(2X~+l) lX(2X~+l)

=4 = 16 = 18 = 16 = 10
e
The relative energy values of the different levels can be calculated as in the case of binuclear
er
1
complexes. Assuming the 5 =- as the ground state with energy 0, the relative energies for
H
2
1 357 9
5 =2' 2' 2' 2 and 2 are 0, -3J, -8J, -15J and -24J respectively.
k
Van-Vleck equation may be applied as in the case of binuclear complexes to calculate XM.
lic
= NAi~2 x(P)
C
XM 3k B T Q
1 3 3 5
P=-x-x2x2xexp(O)+-x-x4x4exp ( -3J) 5 7
- +-x-x6x3xexp ( -8J- )
2 2 2 2 kBT 2 2 kBT
7 9
+-x-x8x2xexp (-
15J 9 11
- ) +-x-xl0xlxexp (-
24J
-)
2 2 kBT 2 2 kBT
= 3 +60exp(3r) + 35 x gexp(8r)+63 x 4 x exp(15r) + 99 x 5 x exp(24r)

2 2
Q = 2 x 2 x exp(O) + 4 x 4 x eXP(~)+6 x 3 x exp(~)

kBT kBT
+8x2xexp -151 ) +10xlxexp (241)

-
( kBT kBT
ry
=4 + 16exp(3r) + 18exp(8r) + 16exp(15r) + 10exp(24r); (r =~)
kBT
ra
Xli = .!XM = N Ag2~2 X (P ) + N A a, (including the TIP)
ib
3 9k B T Q
_ NAg2~2
yl
1 [2+40ex P(3r)+105ex P(8r)+168ex P(15r)+165ex P(24r)] N
- 3k B T x"4
2+Sexp(3r)+gexp(Sr)+Sexp(l5r)+5exp(24r) + AU.
m
5
In the same way for the high spin FellI system having 51 = 52 = 53 = 54 = 55 = with the resultant 2"
he
15 13 11 9 7 5 3 1
5 values 2
(once), (twice), 2 (thrice), 2
(4 times), (5 times), 2"
(6 times), 2"
(4 times), 2" 2" 2"
lc
(twice) with the relative energies -631, -481, -351, -241, -151, -81 and 0 respectively, XM can be
calculated as in the CrllI system. The result is:
ea
Xa = NAg 2~2 X- X -
1 (A) + N a
3k B T 4 B A
th
A = 340exp(63r) + 455exp(48r) + 42gexp(35r) + 330exp(24r) + 210exp(15r)

e/
+ 105exp(8r) + 20exp(3r) + 1
t.m
B = 4exp(63r) + 7 exp(48r) + gexp(35r) + 10exp(24r)

+ 10exp(15r) + gexp(8r) + 4exp(3r) + 1
113
Similarly, the CU~I system (cf Sec. 8.34.1) having 51 =52 =53= 2" 2"
with 5 = (twice) and (once) 2"
e
having the relative energies 0 and -31 can be treated.

er
-1 x -3 x 2 x 2 x exp(O) + -3 x -5 x 4 x exp ( - 31 )
H
NAl~2 2 2 2 2 kBT =NAl~2 x l [I+5ex P(3r)]

XM = 3k T ( 31 ) 3k BT 4 l+exp(3r)
k
B 2 x 2 x exp(O) + 4 x exp -
kBT
lic
=~ = NAg2~2 x~[1+5eXP(3r)] r=J/(k T)

C
i.e. Xa 3 XM 3k B T 4 1 + exp(3r) , B
At ground state (i.e. S = ~) ( assuming no population density at S =%), we have:

IA 1
X = N Ag- .....- x -1 and ~ 2 =-1 g 2~ 2 z ~2 (tak·lng g -- 2 .O· lOB •M• (f
- .
), z.e. J..l - c. S ec. 8 .34 . 1) .
a 3k B T 4 4
(G) Kotani Expression for GroundT-Term from van-Vleck Equation
This aspect has been illustrated for 2T2g term in See. 8.20.3.
Organometallics and Metal Carbonyls:
ry
n-Acid Metal Complexes: Structural and
ra
Bonding Characteristics
ib
yl
m
9.1 INTRODUCTION AND IMPORTANT MILESTONES OF HISTORICAL IMPORTANCE
9.1.1 Definition and Criteria of Organometallic Compounds
he
Conventionally organometallic compounds are characterized by the presence of at least one metal-
carbon bond, i.e. M-C bond where the C-atom belongs to an organic molecule, radical or ion.
lc
Metal carbides are not considered as the organometallics because the corresponding carbon moiety
ea
belongs to the inorganic family.
If the metal centre is linked to the carbon through the bridging atoms like 0, N, S, etc. then such
compounds like [Ti(OR)4]' [Co(en)3]3+, [Co(acac)3], etc. are not regarded as the organometallic
th
compounds.
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The above definition has been extended to cover the following aspects.
(i) Metal carbonyls (having the M-CO bond) and cyanido complexes (having the M-CN bond)
t.m
also belong to the group of organometallics though CO and CN- are well known as the inorganic
moieties. However, some authors include the metal carbonyIs but not the cyanido complexes in
the family of organometallics.
If we follow the definition strictly, the metal carbonyls and the cyanido complexes should be
e
excluded from the dictionary of organometallic chemistry because CO and CN- are not the
er
typical organic substrates.

(ii) The metal-carbon covalent bonds may be either localized (e.g. M-CO bond) or delocalized,
H
i.e. multicentred M-C bonds (e.g. between the metal centre and delocalized 1t-electron systems
as in C 2H4, C6H6, etc.)
k
(iii) The metal-carbon bond may be of ionic nature. The ionic compounds like Na+(C6Hs)3C-,
lic
Ca2+(C sHs-)2 formed by the highly electropositive metal ions with the carbanions stabilized by
delocalization.
C
(iv) In a broad sense, the compounds bearing the nonmetal-carbon bonds (e.g. M-C bonds where
M =B, Si, S, Se, P, or As), are also included in the group of organometallics. Thus, organosilicons,
organosulfurs, organoborons, organoseleniums, etc. constitute an important fragment of
organometallics. However, some authors consider these compounds having the nonmetal-carbon
1295
bonds to constitute a border line of organometallics. If, in the M-C bonds, M represents a
metalliod element (e.g. As, Sb, etc.) then the term organometalliods may be used in place of
organometallics. Electronegativity of hydrogen is almost similar to that of carbon. Thus the dis-
cussion of molecular hydrides and dihydrogen complexes are also included in the area of
organometallics.
Note: In representing the formulas of the organometallics, the IUPAC recommendations (2005) (Sec.
ry
1.15.2) have not been strictly followed here always. In this Chapter, the long standing conventional
practice has been followed for the sake of better understanding of the reactivities and structures of the
ra
organometallics.
ib
9.1.2 Characteristics of the Metal-Carbon (M-C) Bonds
yl
The M-C bonds may be of different types with some characteristics features. These are discussed
below.
m
(i) a-bond: It is the classical 2c-2e M-C bond and it is mainly found in the organometallics of main
he
group elements (i.e. s- and p-block elements) and group 12 (i.e. Zn-family) elements. The exam-
ples are: CH 3MgBr, Mg(CH 3 )2, Ga(CH 3 )3' Zn(C 2H s)2, B(CH 3h, (CH3)3SnCI, CH 3SnCI 3, etc.
(ii) n-acid ligands: It involves the a-donation of the ligand followed by the n-acceptance by the
lc
ligand (e.g. CO, CN-, etc. as the ligands). Sometimes, the n-electron cloud of the BMOs of the
ea
ligands (e.g. C 2H 4, CsH s-, C 6 H 6 , etc.) may be used in a-donation and the vacant n* -MOs of the
ligands participate in metal ~ carbon n-bonding. The organometallic compounds with the un-
saturated organic moieties experience both the 0'- and n- bonding. Such compounds are much
th
more stable than the compounds having only the metal-carbon a-bonds.
e/
(iii) Polarity: The M-C bonds are more polar compared to the C-C bonds. The formation of
M-C bonds can alter the reactivity of the organic moieties.
t.m
(iv) Lewis acidity: Coordinatively unsaturated organometallics (e.g. BR 3, ZnR 2, etc.) can acts as the
Lewis acids. In fact, such alkyl or aryl compounds are highly reactive.
(v) Non-classical bond: In many organometallics, the bonding cannot be explained by the conven-
tionql 2c-2e bonds. It may require the concept of multicentre bonding. This is found in the alkyl
e
compounds of Li, Be, and AI. In the tetramer of LiCH 3, i.e. Li 4(CH 3)4, methyl bridging involves
er
the 4c-2e bonding. In the polymeric form ofBe(CH 3)2, i.e. (BMez)n and dimeric form of AI(CH 3)3,
i.e. A1 2Me6 , the methyl bridging can be explained by 3c-2e bonding.
H
The nonclassical M-C bonding is also noted in the organometallics involving the alkenes, alkynes,
benzene and other ring systems.
k
(vi) Ionic bond: Sometimes, the highly electropositive metal ions can form the ionic bonds with the
lic
carbanions stabilized by delocalization. The examples are: Na+Ph 3C-, Ca 2+(C sH s-)2' etc.
C
9.1.3 Important Milestones in the Development of Organometallics

(cf. Adv. Organomet. Chem., 13, 1, 1975)
• Zeise's salt (1827-31) (a case of serendipity): Zeise, a Danish pharamacist accidentally isolated
[Pt2(C2H4)2CI4] and the salt, K[Pt(C 2H4 )CI 3] . H 20 (known as Zeise's salt) when K 2[PtCI 6 ] reacted
with the boiling ethanol. In fact, before the discovery of Zeise's salt in 1931, the orange coloured
dimeric product [Pt(C 2H 4)CI 2]2 was discovered in 1827. The dimeric product is:
[(112-C2H4)CIPt(fJ,2-rl)2PtCI(112-C2H4)], i.e. [{ Pt(11 2- C2H4)CI(J.!-CI)} 2].
Zeise also prepared [Pt(C 2H 4)CI 2(NH 3)]. However, at the time of Zeise, nothing was known about
the structure of these compounds. In fact, the structure and bonding in the anion, [Pt(C 2H 4)CI 3 ]-
ORGANOMETALLICS AND METAL CARBONYLS: n-ACID METAL COMPLEXES 1297
of Zeise's salt remained unsolved till the fifties of the last century, though Zeise's salt is the first
recorded example in the organometallic chemistry.
• Dimethyl zinc, Zn(CH3)2 (1848): E.C. Frankland, an English chemist, synthesized Zn(CH3)2 in
1848. Then within fourteen years, he prepared several alkyl compounds like Zn(C 2Hs)b Zn(C 2H s)l,
Hg(CH 3)2, Sn(CH3)4, etc. He-used these alkyl compounds, specially the alkyl zinc compounds, in
organic synthesis. Here it is worth mentioning that Frankland first coined the term, organometallic
ry
and it was placed in the vocabulary of chemistry. Frankland's discovery ofZnR 2 may be considered
as the real beginning of organometallic chemistry.
ra
• [Ni(CO)4] (L. Mond, 1888): The volatile compound [Ni(CO)4] was noted by Mond in 1888. It
was produced in the direct reaction between Ni and CO. [Ni(CO)4] was found to decompose to
ib
Ni and CO on heating. These reactions are used in the extraction and purification of nickel.
yl
• [Fe(CO)s] (L. Mond, 1891): It was also first identified by Mond.
• Grignard reagent (RMgX) (1900): The organomagnesium halides (RgMX) were synthesized by
m
Grignard in 1900 and these were widely used in organic synthesis. For this contribution, Grignard
he
was awarded the Nobel Prize in 1912 and the reagent was named as the Grignard reagent to
honour the discoverer.
• Vitamin B t2 and the B t2 -coenzymes (1948): In 1948, the antipernicious anemia factor, vitamin
lc
B 12 was isolated in a crystalline form. It possesses the metal-carbon, i.e. Co-C linkage. It is a
ea
unique example of organometallic compound occuring in nature.
For the determination of the three dimensional structure of vitamin B 12' by X-ray crystallography,
Dorothy Hodgkin was awarded the Nobel Prize in Chemistry in 1964. Vitamin B 12 was synthe-
th
sized by Woodward in 1973.

e/
• Ferrocene, [Fe(n-CsHs)2], (1951-52) (a case of serendipity): Ferrocene, i.e. di-1t-cyclopenta-

dienyliron(ll) was first accidentally synthesized by t",'o independent groups (one group: T. J.
t.m
Kealy and P. L. Pauson, Nature, 168, 1039, 1951; other group: S. A. Miller, J. A. Tebboth and J.
F. Tremaine, J. Chem. Soc., 632, 1952).
Scientific Serendipity
e
The discovery of ferrocene gives an example of Scientific Serendipity (meaning making the
er
fortunate discoveries accidentally). The word serendipity has been coined by Horace Walpole
after his novel, The Three Princes of Serendip that was a Persian fairytale. The three princes of
H
Serendip made the discoveries by accidents according to this novel. Serendip is the Persian and
Urdu name for Sri Lanka.
k
lic
Probably, the chemists of Union Carbide first prepared the compound as the volatile yellow crystals
in 1930 by passing dicyclopentadiene through a heated iron tube. But unfortunately, this observation
C
failed to earn their attention.

In fact, Kealy and Pauson attempted to synthesize the fulvalene type compound in which two
cyclopentadienyl rings will be joined by a double bond. For this purpose, they selected the following
reaction.
2C H MgX + 4Fe3+
s s -----I~ ~
.. - ~ + 2HX + 4Fe2+ + 2Mg2+
(A Grignard reagent) ~
Astonishingly, instead of the fulvalene type compound, they obtained an orange yellow solid
(ClOHlOFe) which is thermally stable up to 400°C. Miller et al also prepared the same compound from
a failed attempt at an organic synthesis of an amine by heating CSH6 in presence of an iron catalyst in
N2-atmosphere. Both the groups proposed the monohapto-structure involving the Fe-C a-bond.
VFeN
ry
H
ra
(Proposed structure of C 10 H 1O Fe
involving two Fe--C bonds)
ib
For the d-block elements, the metal-carbon a-bonded compounds were elusive and many attempts
yl
to prepare such organometallic (a-bonded) compounds went in vein. In fact, chemists were bewildered
with the structure of the very stable compound ClOHlOFe. Finally Wilkinson and Woodward solved the
m
structural problem and it is the ferrocene, an unprecedented sandwich compound in which Cp- binds
as a 11 s-ligand.
he
Discovery of ferrocene initiated a fresh interest in the field of organometallic chemistry. Such orga-
nometallic compounds involving the unsaturated organic moieties experience the metal-carbon
lc
n-bonding and these are much more stable compared to the organometallic compounds bearing the only
metal-carbon a-bonds.
ea
• Within a few months of discovery of ferrocene, Fischer prepared [Cr(C 6 H 6 )2], i.e.
bis(benzene)chromium in the following reaction involving the reduction of CrC1 3.
th
3CrCl3 + 6C 6H 6 + AICl 3 + 2AI ~ 3[Cr(C6H6)2][AICI4]

e/
[Cr(C6H6)2] [AICI4] reduction) [Cr(C 6H 6)2] (a black solid) + AICI4-.

For this contribution, Fischer shared the 1973 Nobel Prize with Wilkinson who made a significant
t.m
contribution in understanding and developing the organometallic chemistry.
9.2 TYPES OF ORGANOMETALLIC COMPOUNDS ONTHE BASIS OFTHE NATURE OF

METAL-CARBON BOND
e
er
Based on the nature and characteristics of metal-carbon bonding, the organometallic compounds can be
classified as follows.
H
(i) Ionic compounds: These are formed by the highly electropositive metals which bind the organic
radical anions electrostatically. The examples are:
Na+Ph 3C-, Ca2+(C sHs-)2, Na+(CsHs-), Mn(C sHs)2' etc.
k
Stability of such compounds depends on the stability of the carbanion which are generally
lic
stabilized through delocalization. In fact, Ph3C- is stabilized through the charge delocalization
over the three phenyl rings. CsHs attains the aromaticity (4n + 2 rule, 6n electrons) to earn the
C
stability.
(ii) Metal-carbon a-bonded compounds: In this type of compounds, 2c-2e M-C bonds are formed.
But due to the electronegativity difference, a partial ionic character is developed in the metal-
carbon bonds. The examples are:
Me3SnX, Pb(Et)4' Zn(R)2 (R = Me, Et), etc. It may be noted that the simple a-bonded
organometallics of transition metals are very much unstable.
(iii) Nonclassically bonded organometallics: In some compounds, the alkyl groups may act as the
bridging groups between the metal centres. In such cases, instead of the normal 2c-2e M-C
bonds, the electron deficient multicentered M-C bonds may be formed.
ORGANOMETALLICS AND METAL CARBONYLS: 1t-ACID METAL COMPLEXES 1299
The examples are:

Li4(CH 3)4 (4c-2e bond); Be(Me)2-polymeric form (3c-2e bond); (AIR3)2-dimeric form (3c-2e
bond), etc.
(iv) Metal-carbon bond having both the 0- and 1t- bonding character: When the ligand (e.g. CO)
can act as a n-acid ligand, in addition to the a-donation by the ligand, there is a n-back bonding
(i.e. metal to ligand) by using the vacant orbital on the C-centre of the ligand. This n-bonding and
ry
a-bonding act in a synergistic fashion to stabilize the metal-carbon bond.
ra
(v) Metal-carbon bonding formed by the 1t-electron of some unsaturated organic moieties: The
n-electron clouds of the unsaturated organic molecular species such as alkene, alkyne, butadiene,
ib
cyclobutadiene, cyclopentadienyl anion, benzene, alkyl anion, norbomediene, tropylium cation,
cyclooctatetraene, etc. can participate in bonding with the metal centre. In such cases~ all the
yl
available n-electrons or a portion of the unsaturated skeleton may participate in bonding.
The number of C-atoms formally gets bound to the metal centre is expressed in terms of
m
haptonomenclature (l1 n ). The examples are:
he
112-C2H4; 113-C3Hs- i.e. 113-allyl; 114-C4Hg i.e. 11 4-butadiene; 114-C4H42- i.e. 114-cyclobutadiene;
l1s-CsHs- i.e. l1S-cyclopentadienyl or 115-Cp; l1s-CsH6- i.e. l1 s-pentadienyl; 116-C6H6 i.e. T)6-benzene;
11 7-C 7H7+ i.e. 11 7-tropylium; 116-C7Hg i.e. 116-cycloheptatriene; 116-CgHg i.e. 116-cyclooctatetraene or
lc
116-cot; 114-CgHg i.e. 114-cot; etc.
ea
The coordination behaviour of such unsaturated organic molecular species has been discussed in
Sec. 9.20.
th
Here it is worth mentioning that the above ~entioned unsaturated organic molecular species can act
as the n-acid ligands by using their vacant n* -MOs into which the metal centre can push the electron
e/
density.
t.m
9.3 EFFECTIVE ATOMIC NUMBER RULE: EIGHTEEN ELECTRON (18e) RULE: SIXTEEN
ELECTRON (16e) RULE
This aspect is quite important in understanding the molecular and electronic structures of the complexes
e
including the organometallic compounds. This has been illustrated and discussed in detail in Secs. 3.3,
3.17.5,9.4.3, and in Sec.12.8.5 of Vol. 3.
er
9.4 METAL CARBONYLS

H
9.4.1 Introduction
k
We have already mentioned that in terms of strict definition, the metal carbonyls are excluded from the
lic
organometallics because CO is an inorganic moiety. However, many authors include these in the family
of organometallics.
C
[Ni(CO)4]' a volatile carbonyl was noted by L. Mond in 1888. It was produced in the reaction
between nickel and CO. It readily decomposes to Ni and CO on heating at about 180°C. Formation and
decomposition of [Ni(CO)4] is the basis of extraction and refining of nickel in Mond's process. Another
carbonyl, [Fe(CO)s] also dates back in history and it was also identified by L. Mond in 1891.
CO acts as a potential1t-acid ligand and stability of the metal carbonyls depends on the feasibility
of metal to ligand n-bonding. This is why, the metal carbonyls mainly involve the transition metals
which allow the m-back bonding. In fact, the metal centres in low-positive, zero and even negative
formal oxidation states are the best candidates for the formation of metal carbonyls. The metal centres
. with high positive oxidation states, heavier transition metals and late members of a particular
series fail to form the stable carbonyls because their increased electronegativity disfavours the
metal to ligand n-back bonding.
Borane carbonyl, H3BCO is the only example of carbonyl formed by a main group element. It has
been argued that stability of this compound depends on the hyperconjugation of the adduct.
H"
ry
8=== C=== 0 ........--~~.
ra
H/H+
The veo value (::::: 2165 em-I) found in the adduct indicates that veo is increased compared to that of
ib
free CO (veo ::::: 2145 em-I). It indicates that the hyperconjugation is not very much important in the said
yl
adduct.
Note: K6(CO)6 obtained in a reaction between K and CO is not a carbonyl. It is a derivative of C6(OH)6
m
(hexahydroxybenzene).
he
9.4.2 Different Types of Carbonyls and Their Properties
Besides the mononuclear carbonyls, carbonyl clusters are well known. The carbonyl clusters containing
lc
upto four metal centres are described as the low nuclearity carbonyl clusters (LNCC) while the
carbonyls having five or more metal centres are called the high nuclearity carbonyl clusters (HNCC).
ea
Sometimes, the mixed ligand metal clusters having the other ligands like NO, cyclopentadienyl, etc. are
known. Sometimes, the metal clusters may be extended by heteroatoms like C, N, S, etc. These aspects
th
of carbonyl clusters have been discussed in Sec. 12.8.5. of Vol. 3.

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Table 9.4.2.1 Some representative metal carbonyls (see Figs. 9.4.2.1 and 12.8.5.1 of Vol. 3, for structures)
t.m
• Mononuclear carbonyls: [Ni(CO)4]' [Ru(CO)s], [Fe(CO)s], [W(CO)6]'

[MO(CO)6], [Cr(CO)6], [V(CO)6]'
• Binuclear carbonyls: [Mn2(CO)1O], [ReiCO)lO], [FeiCO)9], [Co 2(CO)g],
[Rh 2(CO)s], [Ir2(CO)s]·
e
• Trinuclear carbonyls: [Fe3(CO)\2], [OS3(CO)\2], [RU 3(CO)\2]

er
• Tetranuclear carbonyls: [Co 4(CO)\2], [Rh 4(CO)\2], [Ir4(CO)\2], [OsiCO}J

(x = 14, 15, 16)
H
• Pentanuclear carbonylates and carbonyls: [Ni s(CO)\2f-, [OsS(CO)\6]

• Hexanuclear carbonylates and carbonyls: [Rh 6(CO)\6], [Os6(CO)\sf-, [Co6(CO)\sf-, [Co 6(CO)\4]4-
k
• Polynuclear carbonyls of Os: [OsS(CO)\6] (TBP), [Os6(CO)lld (Capped TBP)

lic
[Os6(CO)\sf-(Oh), [Os7(COhIl (Capped 0h)

[OS8(CO)22]2- (bicapped 0h)
C
• . Carbonyl hydrides: [HMn(CO)s], [H 2Fe(CO)4], [HCO(CO)4], [H 2Fe3(CO)\ d
(A) Formula representation of the carbonyl hydrides: The hydrogen(s) present in these com-
pounds may show the protonic character (i.e. Bronsted acidic property) or the hydridic character
depending on the nature of the system. If they are considered as the Bronsted acids, then they should
be represented as follows:
Bases
[CO(CO)4]-, [Fe(CO)4]2-,
[Mn(CO)s]- ,etc.
If 'H' is considered as the H- ligand (i.e. 2e donor ligand in electron count), then they should be
represented as follows:
[CO(CO)4H], [Fe(CO)4H2], [Mn(CO)sH], etc. «(1 IUPAC 2005 convention; Sec. 1.15.2 to determine
the ligand order).
However, conventionally, they are still represented in the leading textbooks as follows:
ry
[HCO(CO)4], [H 2Fe(CO)4], [HMn(CO)s], etc.
• Carbonyl halides (Sec. 9.4.18): [Mx(CO)yX z] satisfy the EAN rule (M = most common metals
ra
forming the binary carbonyls and the metals like Pd, Pt and Au which generally do not form the
ib
binary carbonyls). Examples: [Pt(CO)CI 2]2' [MnBr(CO)4]b [Au(CO)CI], [Fe(CO)4I2], [Ru(CO)4I2],
[Rh(CO)2I2]-' [Rh(CO)2CI]b [Re(CO)4I]b [Re(CO)sI], etc .
yl
• Heteropolynuclear or mixed metal carbonyls: [MnCo(CO)9], [Mn2Fe(CO)14], [RuFe2(CO)12],
m
[Ru2Fe(CO)12], [FeCo 3(CO)12]-' [HRe2Mn(CO)14], etc.
he
Isostruetural and isoelectronic earbonyls and earbonylate anions
Octahedral: [Ti(CO)6]2-, [V(CO)~-, [Cr(CO)6]
lc
Trigonal bipyramidal: [V(CO)S]3-, [Cr(CO)s]2-, [Mn(CO)s]-, [Fe(CO)s]
ea
Tetrahedral: [Cr(CO)4]4-, [Mn(CO)4]3-, [Fe(CO)4]2-, [CO(CO)4]-' [Ni(CO)4]
All these conform to the 18e rule. A 2e donor CO group is equivalent to 2e i.e. one CO group may
th
be replaced by adding 2e. Thus, [Ti(CO)7] is isoelectronic with [Ti(CO)6]2- but [Ti(CO)7] is unknown
probably due to the steric reasons. [Ti(CO)6]2- is also quite unstable and it can be trapped by using
e/
the large cations like (K-Crypt-222)+ i.e. [K(C-222)]2[Ti(CO)6]' In fact, the highly reduced
carbonylate anions like [Cr(CO)4]4-, [Mn(CO)4]3-, [V(CO)s]3-, etc. are also quite unstable.
t.m
The metal centres do not like such a high accumulation of negative charges though the metal ~ CO
n-back bonding reduces the load of negative charge on the metal to some extent.
Carbonyl hydrides (cf. Sees. 9.4.17,10.1,10.4)

e
Carbonylate anions can act as the Bronsted bases and their conjugate acids e.g. [HMn(CO)s],
er
[HCO(CO)4], [H 2Fe(CO)4], etc. are described as the carbonyl hydrides. But some of these
protonated species may also act as the fairly strong acids (cf. Sections 9.4.7E, 10.1, 10.4). PMR
H
spectra (B = -5 to -15 ppm) the carbonyl hydrides have been discussed in Sec. 12.2.6.
k
(B) Polynuclear carbonyls: Structures of some representative polynuclear carbonyls are given in
lic
Fig. 9.4.2.1 and in Fig. 12.8.5.1 (Vol. 3).

C
00 o 0
OC", /C C", /CO Oc",~/CO
'" '"
OC-Mn-Mn-CO OC-Fe - Fe-CO
OC / C C
00
/ co OC
/ "'" C/
o ' "CO
[Mn 2(CO)10]
(Linear)
o o 0
C
CO
oc'" / I OC",M.,/co
OC-Co - Co -CO _____Co - Co- CO
OC / - '"
I
C OC / '"CO OC CO
ry
o
[Co 2(CO)a], in solution [Co2(CO)al, in solid state
ra
i. e. [C02(CO)6(f..l2-CO)2]
ib
o o
yl
C C
3c-2e M-H-M
g OC",I/CO g I/CO.
)nd ]
m
I
I.~."
bridge 2-
OC Fe (2)
. ". , OC I CO
'" I ~I
H oc'" M' M " " CO
he
~Fe ""
(18ey "'(18e) Fe OC CO
[
(OC)4Cr", H/ cr(CO)4 OC/ (1)~ OC/ I ... ~M-CO
[H 2Cr2(CO)a] 2-
g lc
OC/ "co I g . . I "'co
C C
ea
(No metal-metal bond) o o
[Fe3 (CO)12] i.e.
th
[Fe3 (CO)10(f..l2-eO)2]
e/
CO CO
O~I/CO oc"" I,/co

t.m
CO
Fe
I ~Fe""
f~\ /CO
oc'"
Ru~1 C=O OC'" /
OC/ I ~Fe/
e
OC-Ru Ru-CO
"" '"
er
CO OC/ I "'co oc/ CO /

CO CO
CO
H
[RuFe2(CO)12]' (mixed metal carbonyl) [Ru 2Fe(CO)12]

Mixed metal carbonyl
k
lic
C
3c-2e M-H-M
Mn(CO)s bridge bond
/
(OC)4Re-H-Re(CO)s
~
[(OC)sCr - H - Cr (CO)s]-
ry
(18e) (18e)
[HRe2Mn(CO)1J
ra
(Mixed metal carbonyl) [HCr2(CO)10]-
ib
yl
m
he
lc
ea
th
e/
t.m
e
er
H
2-
co CO
k
OC CO OC CO OC CO
\/ \/ \/ oc""I I/co
lic
OC-M M M-CO Co---Mn-CO
/\ /\ /\ oc/I I""co
C
OC CO OC CO OC CO CO CO
[M 3 (CO)1J 2- (M =Cr, Mo, W) [MnCo(CO)gl

[ (OC)sMn - Fe(CO)4 - Mn(CO)s ] (Heteropolynuclear or mixed
metal carbonyl)
[Mn 2Fe(CO) 14l
(Mixed metal carbonyl)
o
oc",l/cO ~
C
2-
Ir
oc"'/ \/co OC~\\CO

@-Fe~?-@
ry
OC-Ir Ir-CO
oc/\ / "'CO ~Fe
ra
Ir
8@;
ib
oc/I"'co CO
yl
[Fe4 (Jl4-e)(CO)12]2-
[lr4 (CO)12]
m
(Butterfly)
he
2- 2-
CO
oc I CO
CO
"'/
Ae
lc
OC"'" \./J ~ CIO
ea
CO
l1800~
Ae
~
CO
V /
th
OC/j O AI e",
C / CO
o /~
e/
CO
Ae
OC/I"'-co
t.m
CO
[Re 4( CO)16]2-
e
er
Ni
c/I"'c
H
o C 0
o
[N i6( CO )g(Jl2-eO )3]2-
k
lic
C
co co CI
I/X"'- I/CO
oc"'- OC""- / ~ /CO
M M M M
OC/ I"'-X/ I"'-CO OC/ ~CI/ ""'CO

co CO
ry
[M(CO)4X]2 (M = Re, Os, Mn), X =Br, I [M(CO)2CI]2 (M = Pt, Rh)
ra
000
ib
C C C
" Au1/
yl
~
m
he
CO
OC I Au
~/~
lc OC -
/ ~'~1
'"
- - - - - - - - - - C- - - - - - - - - - Au
/CO
'CO
ea
OC Au I
OC :I
I
!/
th
OC C /CO
o :V
e/
Au
OC
/ "'- CO
t.m
[Ru 6(Jl6-C)(CO)16(Jl2-CO ))
o
e
C
°c I CO (CO)4
)~Os(CO). '::::os~
er
r7 ~f
0 0 Os
(OC)Ps~~~/ 0c" /cO / ~

H
Os Os Os (OC)30S OS(CO)4
~............... ....../
k
1
(CO).
[OS4(CO)16]' (puckered)
OC/ COl , ...... ~ /... .. 0
C ""-CO \ /
lic
(cyclobutane analogue) .. 'Os . . Os

c/ I "'"C (CO)4
ago
C
[OS4(CO)1S]' (planar OS4 unit)
[OS4(CO)1J
(Semibridging by CO)
Fig.9.4.2.1 Some representative structures of polynuclear metal carbonyls (Note: [OsiCO)J (x = 14,15,16) obeying
18e rule; Os-Os bonds =4(x = 16), 5(x = 15), 6(x = 14 with 4 semibridging Jl 2-CO groups). Sec. 9.4.6 for the properties
of the semibridging CO groups.
(C) Special properties of the mononuclear carbonyls: These are generally colourless or lightly
coloured volatile liquids. In some cases, they may be solid, e.g. [M(CO)6]' M = V, Cr, Mo, W. In such
compounds the M-C bonds are not very much strong (bond energy: - 150 kJ mol-I). The M:-.:.CO
bond energy is relatively higher for the heavier congeners in a group and it is also higher for the late
members in a series.
Because of th~ low M-C bond energy, they undergo decomposition easily upon heating or irradiation
with the ultraviolet (UV) light and release CO. This is why, such carbonyls are to be handled care-
fully to avoid poisoning by CO. In fact, [Ni(CO)4] is several hundred times more toxic than CO
ry
because inhalation of [Ni(CO)4] can cause nickel-plating in lungs through the decomposition of
[Ni(CO)4]·
ra
In general, they behave like the typical covalent compounds and they are soluble in nonpolar hydro-
carbon solvents. .
ib
yl
Table 9.4.2.2 Properties of some representative binary earbonyls
m
[V(CO)6] dark green crystals; yellow orange in solution; sublimes in vacuum; decomposes at
70°C; octahedral geometry; paramagnetic ( I e); air-stable.
he
[Cr(CO)6] colourless crystals; sublimes in vacuum; air stable; decomposes at 180°-200°C.
[MO(CO)6]
[W(CO)6]
}: octahedral structure. M-CO bond dissociation energy (kJ mol-I) increases in the sequence:
[Cr(CO)6] (109) < [MO(CO)6] (151) < [W(CO)6] (176) (cf v eo almost the same; many other
lc
f~ctors to determine the bond dissociation energy are to be considered; see Q. 40)
ea
[Fe(COh] light yellow liquid; m.p. -20°C; b.p. 103°C; trigonal bipyramidal geometry; action
of UV gives [Fe2(CO)9]'
[Ni(CO)4} colourless liquid; m.p. -25°C; b.p. 43°C; tetrahedral geometry; very toxic; flammable;
th
decomposes at 180°C to metal.

[Ru(CO)s] colourless liquid; m.p. -22°C; difficult to purify; trigonal bipyramidal geometry.
e/
[MniCO)10] . . golden yellow crystal; m.p. 151°C; sublimes in vacuum; heat and air sensitive.
t.m
[Fe2(CO)9] yellow solid; m.p. 100°C; insoluble; nonvolatile;

[Fe3(CO)12] deep green crystal; m.p. 14D-150°C; decomposition; moderately soluble; air sensitive.
[RU3(CO)12] orange; m.p. 150°C; decomposes;
yellow; m.p. 224°C; air-stable;
e
[OS3(CO)12]
[C0 4(CO)12] black crystal; decomposes at 60°C; air-sensitive.
er
[Rh 4(CO)12] red crystal; decomposes at 150°C; sublimes in vacuum; air-stable.

H
[Ir4(CO)12] yellow solid; decomposes at 230°C; air-stable.
(D) Colour of the carbonyls: Generally, the mononuclear carbonyls are almost colourless but the
k
polynuclear carbonyls are coloured and intensity of the colour increases with the increase of the
lic
number of metal atoms. Electronic transitions among the orbitals mainly localised on the metal frame-
work (cf. PSPT) give the colour of the polynuclear carbonyls.
C
(E) Homoleptic products: In metal carbonyls, the CO group can be substituted by the other 1t-acid
ligands. When all the CO groups are substituted by only one type of ligands, it leads to the homoleptic
products. It is illustrated below.
[Ni(CO)4] vs. [Ni(PF 3 )4]; [Ni(CO)4] vs. [Ni(CNR)4]; [V(COj~f+ ~s. [V(CNR)6]+; [Pt(CO)4] vs.
[Pt(PPh 3 )4];
9.4.3 Application of the 18-Electron (18e) Rule to Metal Carbonyls

This aspect has been already discussed in general in Sees. 3.3, 3.17.5 and Sec. 12.8.5 of Vol. 3 of this
book. Here we shall mainly discuss only some limited points.
(i) Relatively unstable carbonyls formed by the early members of transition series: The early
members (e.g. Gr. 4 or IV A, 5 or V A, etc.) of the transition series bear relatively fewer number
of d-electrons (say 2,3 d-electrons). To satisfy the 18e configuration for such transition metals, it
requires a relatively larger number of CO ligands (i.e. a relatively larger coordination number).
This required larger coordination number is disfavoured due to the steric factors. This is
why, the carbonyls (e.g. [Ti(CO)6]2-) formed by the early members of the transition series are
ry
relatively unstable. The unstable species [Ti(CO)6]2- can be isolated with the large counter cations
like (K-Crypt-222)+ i.e. [K-Crypt]~+[Ti(CO)6]2-. .
ra
(ii) Reaction pathways in the mononuclear carbonyls (cf. Sec. 10.2): If the 18e rule is satisfied in
ib
a particular metal carbonyl then the reaction intermediate or transition state will not have the
electron count at the valence shell of the me~al more than 18. The product will also satisfy the 18e
yl
rule. It is illustrated for the following reaction.
m
[Cr(CO)6] + L ~ [Cr(CO)sL] + CO (L = 2e donor ligand like CI-, PR3, R 2S, etc.)
If the reaction passes through the associative mechanism, then the electron count at the valence
he
shell of 'Cr' in the intermediate or transition state [Cr(CO)6L] will be 20. This is not expected. On
the other hand, if the process passes through the dissociative mechanism, then the valence
lc
electron count at the intermediate or transition state [Cr(CO)s] will be 16. Thus, the dissociative
path is more favourable because the 16e- intermediate is more stable than the 20e- intermec!i_ate (cf.
ea
Sec. 9.3). In fact, the above ligand substitution process passes through the dissociative path.
Because of the same ground, CO-substitution at [W(CO)6]' [Fe(CO)s], [Ni(CO)4]' etc. (all
th
satisfying the 18e rule) occurs through the dissociative path.

This aspect has been discussed in detail in Sec. 10.2. Two electron reduction of [Fe(CO)s] (18e
e/
configuration) produces the tetracarbonyl dianion [Fe(CO)t1,]2-( 18e configuration) with the expul-
t.m
sion of one CO group.

[Fe(CO)s] + 2Na ~ Na2[Fe(CO)4] + CO
(iii) Limitation of the 18e rule in the p~lynuclear carbonyls and failure to identify the nonbridged
e
and bridged carbonyls: In the p~lynuclear carbonyls, the 18e rule is found true in many cases.
er
It has been illustrated in Sec. 3.3 and in Sec. 12.8.5 of Vol. 3. In terms of electron count, the
bridging and nonbridging CO groups cannot be distinguished. This aspect is illustrated in the
H
following section.
[Rh(CO)2CI]2' [Ir(CO)CI(PPh)2] (Vaska's complex), etc. follow the 16e rule (cf. Sec. 9.3).
k
lic
9.4.4 Characteristic Features of the Bridging and Terminal CO Groups: Factors

Favouring the Nonbridged or CO Bridged Structures (cf. Fig. 9.4.14)
C
In the polynuclear carbonyls, there are two types of carbonyl groups: bridging and nonbridging (i.e.
terminal). The bridging and nonbridging CO groups can be recognized by their IR spectra. The bridg-
ing CO groups are of two types i.e. doubly bridging and triply bridging. These are illustrated in Fig.
9.4.4.1. Doubly bridging CO groups are commonly found while triply bridging CO groups are found
in some limited cases e.g. [Rh6(CO)6] which is [Rh6(CO)I2(Jl3-CO)4].
In the polynuclear carbonyls, the bridging CO groups generally occur in pairs. We can consider
the two isomeric fragments as in Fig. 9.4.4.1 b. In terms of electron count, both the fragments are
equivalent. Each terminal group acts as a 2e-donor while the doubly bridging CO group contributes
one electron to each metal centre. Thus the 18e rule cannot distinguish the possibilities.
:0:
(1l1-CO) em:
II (c
II
0
iXJM -90~
C
M~
.. I
M c'\-
M M-M
/c~ -90~ I ..
ry
M M
C
II
cJ
ra
Doubly bridging
CO i.e. Jl2-CO
Triply bridging 0 :0:
~;J
ib
CO i.e. Jl3-CO (Bridging CO)
\. ) (Terminal CO) )
\.
Y 'Y"
yl
(a) (b)
m
Fig.9.4.4.1 (a) Two types of bridging CO groups~ (b) Bridging-terminal tautomerism leading to two isomeric fragments.
he
Relative stability of the isomeric segments due to th@ terminal-bridging tautomerism of the CO
groups depends on the size of metal atoms. For the larger metal atoms, the larger M-M distance
disfavours the CO group to bridge along the M-M segment. lc
To sit a bridging 1l2-CO group along a longer M-M bond, it will have to exercise the following
ea
disfavourable factors.
(i) M-C -M bond angle to open up and/or, (ii) M-C bond to elongate.
th
These will destabilize the system. Elongation of the M-C bond will weaken the both 0'- and
1t- bOEding interactions. Normally, the M-C -M bond angle lies close to 90° (cf in saturated ketones~
e/
C-C -C ~ 120°, where no electron delocalization with the )CO group occurs). In the carbonyls, the
t.m
bridging CO group participates in electron delocalization through the metal t!-orbitals (cf Fig.
9.4.9.3). This electron delocalization gives the stability of the system. If the M-C -M bond angle
becomes significantly greater than 90° then the electron delocalization process gets seriously ha~pered
to destabilize the system. This is why, the longer M-M distance which will open the M- C -M
e
bond angle more disfavours the bridging of a CO group as a bridging 1l2-CO along the M-M
er
bond.
H
Factors controlling the position of the nonbridged-bridged tautomeric equilibrium

k
o
lic
/C'"
OC-M-M-CO ~ M--M
C
"'c/
o
• Longer M-M distance disfavours the bridged structure because of opening up of the
M- C -M bond angle () 90°) and elongation of the M-C bond. Thus the heavier congeners
prefer the nonbridged structure.
• Coordination number increases in the bridged structures to increase the steric crowding.
This steric crowding is not important for the heavier congeners but important for the lighter
congeners.
In fact, the heavier congeners (which are larger in size) prefer the nonbridged structures over the
bridged isomeric structures.
• [Fe3(CO)12] vs. [M3(CO)12] (M = Ru, Os): For example, in [Fe3(CO)12] there are two bridging
CO groups while in [RU3(CO)12] or [OS3(CO)12] there is no bridging CO group (cf. Fig. 9.4.2.1)
i.e. in [RU3(CO)12] or [OS3(CO)12], all the 12 CO groups are the terminal CO groups. In
[RuFe2(CO)12], two bridging CO groups lie along the Fe-Fe bond while in [Ru2Fe(CO)12],
ry
there is no bridging group. It indicates that the CO group does not bridge along the Ru-Ru or
ra
Ru-Fe bond in the mixed metal carbonyls (Fig. 9.4.2.1). These are quite expected.
• [M4(CO)12] (M = Co, Rh) vs. [Ir4(CO)12]: In M 4(CO)12 (M = Co, Rh) there are three doubly
ib
bridging CO groups while in the corresponding carbonyl of the heavier congener, i.e. [Ir4(CO)12]
there is no bridging CO group (cf. Fig. 9.4.2.1).
yl
• [Fe2(CO)9] vs. [OS2(CO)9]: In [Fe2(CO)9] there are three bridging CO groups while in [OS2(CO)9],
m
there is only one bridging CO group. It suggests that the heavier congeners prefer the less bridg-
ing CO group.
he
• [Mn2(CO)10] vs. [C0 2(CO)s]: [Mn2(CO)IO] adopts the nonbridged structure, i.e.
[(OC)5Mn-Mn(CO)5] while for [C0 2(CO)8], there is an equilibrium mixture of the bridged and
lc
nonbridged structures. In the mixed metal carbonyl, i.e. [MnCo(CO)9]' there is no bridging CO
group.
ea
[(OC)5Mn-Mn(CO)5]; [(OC)5Mn- Co(CO)4]
o
th
II
e/
/c""
t.m
(OC)4CO - CO(CO)4 ~ .. (OC)3 CO "", /CO(CO)3

(No bridging CO) "C (Solid)
(Solution) II (2~2-CO)
e
o
er
[C0 2(CO)s] (solid state): veo (cm- l )= 2075, 2064, 2047, 2035, 2028 (for the terminal CO groups)
= 1867, 1859 (for the J.l2-CO groups)
H
The structural difference between [Mn2(CO)IO] and [C0 2(CO)8] can be explained by considering the
relatively smaller atomic size of Co compared to that of Mn. For the d-block elements, in moving from
k
left to right along the period, the atomic size gradually decreases due to the increasing trend of effective
lic
nuclear charge experienced by the outermost electrons.

Here it is worth mentioning that besides the metal-metal distance factor, the steric factor (cf. Sec.
C
9.4.1 0) is also important to explain the relative stability of the bridged and nonbridged tautomers. If
[Mn2(CO) 10] adopts a bridged structure like [Mn2(CO)8(J.l2-CO)2] then the coordination number around
Mn becomes 7 (cf. coordination number depends on the number of J.l2-·CO groups) which is sterically
disfavoured. On the other hand, in the bridged structure, [C02(CO)6(J.l2-CO)2], the coordination number
is 6 which is likely. In fact, [V(CO)6] (17e configuration) declines to dimerize to attain the 18e
configuration because it will lead to coordination number 7 which is sterically disfavoured. It may be
mentioned that the steric factor is only important to the carbonyls of lighter congeners. Based on
the above arguments, the mixed metal carbonyl [MnCo(CO)9] is expected to adopt the nonbridged
structure. [(OC)5Mn-Co(CO)4] and it really happens so (Fig. 9.4.2.1).
• [Fe2(CO)9] vs. [Fe3(CO)12] (Fig. 9.4.2.1): In [Fe2(CO)9] i.e. [Fe2(CO)6(1l2-CO)3] there are three
bridging CO groups to provide the coordination number (C.N.) 7. On the other hand, in [Fe3(CO)12]
i.e. [Fe3(CO)1O(1l2-CO)2] there are two bridging CO groups to provide C.N. 7 (to two Fe-centres)
and 6 to the remaining Fe-centre. If the number of bridging CO is further increased in [Fe3(CO)12]
it will make C.N. >7 which is sterically disfavoured. This is why, in moving from [Fe2(CO)9] to
[Fe3(CO)12], the number of bridging CO groups decreases.
ry
OC~ /CO
ra
Oc--?co~\/CO
ib
I/
OC"",
Co - /1Co . . .
yl
CO
-OC/\~ ~CO
m
c--Co
o oc / "co
he
(4~-CO)
lc (solution)
ea
• Tautomeric structures of [C02(CO)s] and [C04(CO)12]: It has been noted that for [C0 2(CO)g],
the bridged structure predominates in solid state while in solution, the nonbridged structure
predominates. Similarly, for [C04 (CO)12], a tautomeric equilibrium between the two tautomeric
th
forms (differing in the number of bridging CO groups) is established.

e/
• Tautomeric structures of [Fe3(CO)12]: A similar tautomeric equilibrium also prevails for

[Fe3(CO)12] involving the bridged structure (21l2-CO) and nonbridged structure.
t.m
oc co co .
",1/ co
/JFe /
~f~co
e
OC~F~CO Clo
co
er
OC
oc ~/
OC~ /I~co oc""" ~o~r
H
"""0l CO
k
/I~
lic
oc co co / "'CO
OC
C
(2 ~-eO) (No bridging CO)

(solid) (solution)
Here it is worth mentioning that energies of the bridged and nonbridged tautomers are very much
comparable in the binuclear and polynuclear carbonyls. The fluxional character leading to the
intramolecular rearrangements and scrambling of CO groups over the two or more metal centres occurs
due to the such tautomeric equilibrium. These aspects have been discussed in Sec. 10.11.
9.4.5 Fluxionality (i.e. Stereochemical Nonrigidity) in Carbonyls

These aspects have been discussed in detail in Sec. 10.11.
ORGANOMETALLICS AND METAL CARBONYLS: It-ACID METAL COMPLEXES 1311
9.4.6 Coordinating Behaviours of the CO Groups in Carbonyls

(i) Terminal CO group: It acts as a 2e donor ligand to a particular metal centre i.e. Mf-C=O.
However, besides the ligand to metal a-donation, the 1t-back bonding plays a crucial role in the
metal-carbon linkage as usual.
(ii) Bridging CO group: Like the terminal CO groups, the bridging CO groups act also as the 1t-acid
ry
ligands. It has been already mentioned that the bridging CO groups are of two types: doubly
bridging (Le. 1l2-CO) and triply bridging (i.e. 1l3-CO) (cf Fig. 9.4.4.1). The triply bridging CO
ra
groups are also described as the apical bridging.
The doubly bridging CO groups (Le. 1l2-CO) are more common than the triply bridging CO
ib
groups. It is found only in some limited cases like [Fe4(1l3-CO)4(llS-Cp)4], [Rh6(CO)6] i.e.
yl
[Rh6(CO)12(1l3-CO)4] (Fig. 9.4.2.1). The 1l2-CO groups are generally placed symmetrically between
the two metal centres. However, in some rare cases, the unsymmetrical bridging is known.
m
o
~~
he
a;t: ~,
a= ~, unequal M-C
Equal M-G bond lengths i. e. a ;t: b
bond lengths
M . -90 0 M
lc
ea
(symmetrical ~-CO) (unsymmetrical or semibridging ~-CO)
th
In a symmetrical 1l2-CO, the M-C bond lengths are equal while in an unsymmetrical 1l2-CO, the
M-C bonds lengths are unequal. Unsymmetrical 1l2-CO groups are considered to represent
e/
the intermediate nature of the terminal and bridging CO groups. This is why, such bridging
CO groups have been described as the semibridging 1l2-CO groups. The geometrical features of
t.m
structure, steric factors and electronic effects determine the nature of 1l2-CO group. In [OS4(CO)14],
(Fig~ 9.4.2.1), there are four semibridging 1l2-CO groups. It may be noted that depending on the
condition, 1l3-CO groups may be symmetrical or unsymmetrical.
e
In some limited cases (e.g. [HFe4(CO)ls]-), it has been noted that one CO group interacts with
er
the 4 metal centres. It binds with 3 metal centres through the C-end (i. e. like a 1l3-CO group) and
simultaneously it binds with the 4th metal centre through the 1t-electron cloud of the CO mol-
H
ecule. In such cases, the CO groups can be considered as the 4e (20 + 2x) donor ligands.
Electron counting for the Jl2-CO and J.l3-CO groups: For the 1l2-CO groups, each CO group
k
donates one electron to each of the two metals. Thus, a 1l2-CO group also acts as a 2e-donor
lic
ligand. For the 1l3-CO groups, each CO group may be considered to donate one electron to each
of the two metals and none to the third metal centre. In this line of argument, the bond with the
C
third metal centre arises from the electrons supplied by the metal. However, when a 1l3-CO group
binds symmetrically (i.e. all the three M-C bonds are equal), the concept of multicentre bonding
(i.e. the 4c-2e a-bonding) is quite reasonable.
(iii) Side-on bonding by the x-electron of CO (cf Fig. 12.1.17.1): The 1t-electron cloud may be used
for coordination. It may happen in different possible ways.
Side-on bonding from CO by using the 1t-electron cloud is known only in some limited cases.
4e-donor (2a + 2x) property of CO is known to occur in [Mn2(CO)s(dppm)2] (dppm =
bis(diphenylphosphino)methane, i.e. methylenebis(diphenylphosphane) and 6e-donor (2a + 4x)
property of CO is found in [Nb3(CO)7(l1s-Cp)3] .
Almost linear
bridging CO 0 M
~P 9t\P #~ 111----- \
/C \-/ ,/C-~M /C~M
M M M~/ M~M/
ry
(2a + 21t) donor M
(2a + 21t) donor
ra
(2a + 41t) donor (ct. [HFe 4 (CO)1S]
ib
(iv) Carbon-oxygen bond order in different modes of bonding (see Figs. 9.4.9.2, 3): For the termi-
nal CO groups, the bond order in the C-O linkage is expected to be 3 as in free CO in terms of
yl
only ligand to metal a-bonding (involving the nonbonding electron pair of CO) but because of the
m
metal ---7 CO n-back bonding involving the vacant n* -MO of CO, the bond order is less than 3.
For the J.12-CO group, the bond order in the C-O linkage is approximately close to 2.
he
Approximately, a J.!2-CO group may be compared with the )CO group of a saturated ketone.
However, the ketonic )CO group and bridging J.!2-CO group of metal carbonyls differ in the
following aspects. lc
R M
tc=o
-90 0
~
ea
V
eo ~ 1715 cm- 1 -120 0 (:C=O I v eo 1750-1900 em-1
RY(ketone) M0~-co)
th
'"
e/
• In the ketones, C-C -C bond angle is approximately 120° while in the metal carbonyls, the
M- C -M bond angle is approximately 90° and in such cases the metal-metal bond is generally
t.m
present.
• In the metal carbonyls, an extensive electron delocalization by involving the metal d-orbitals, and
both cr (which is predominantly nonbonding) and n* -orbitals of CO prevails. This electron
e
delocalisation leading to",M(d) ---7n*-MO(CO) back bonding for the J.!2-CO group decreases with
er
the opening of the M- C -M bond angle from 90°. This type of electron delocalization is absent
in the saturated ketones i.e. R 2CO having the bond angle about 120°.. For the apical or triply
H
bridging CO (i.e. J.!3-CO) group, the carbon-oxygen bond order is as low as 1. This very low bond
order arises due to the participation of three metal centres for the metal---7CO n-back bonding by
k
using the vacant n*-MO of CO.

lic
In terms of Lewis acid-base adduct formation, the bridging J.!2-CO group may be considered as
a dianion (: ~=or- having two lone pairs of electron on carbon. This dianion is isoelectronic
C
with 02. The dianion C0 2- formation leads to the development of positive oxidation state on the
metal centre in the neutral metal carbonyls. The dianion C0 2- then donates two electrons to each
of the two metal centres. The bridging J.!3-CO group may be accordingly treated as a tetraanion
(: ~- 0 )4- which is isoelectronic with 0]- (peroxide). This tetraanion uses the three lone pairs
of electrons for the interaction with the three adjacent metal centres (i.e. one lone pair to be
donated to each metal centre). This concept expects the C-O bond order as 2 and 1 in Jl2-CO and
J.!3-CO groups respectively.
o
II C
M-C:=O
(1l1-GO) /~M
M~/
ry
M
ra
C-O bond order} terminal ) doubly bridging * ) triply bridging
and vC-O 1850-2140 cm- I 1700-1850 cm- I 1600-1720 cm- I .
ib
(* cf - 1715 cm-I for the saturated ketones)
yl
The bond order and v eo depend largely on the ease of metal ~ CO n-back bonding.
m
(iv) Coordination through the O-end of CO (cf Sec. 9.4.9 for details): Generally, CO binds with the
metal centre through the C-end. Though the lone pair resides on both the C- and O-ends, because
he
of the electronegativity ground, coordination through the C-end is favoured. In terms of the MO
energy diagram of CO (cf Chapter 9 of Vol. 2), it appears that the lone pair residing on the C-end
lc
is basically nonbonding in character and it is predominantly enriched in p-character. The lone pair
ea
residing on the O-end is also nonbonding in character but it is predominantly enriched in
s-character. This is why, the lone pair on the C-end is more suitable for donation. Besides this, the
vacant n*-MO of CO is basically concentrated on the C-end and thus the the metal (d) ~ n*(CO)
th
n-back bonding is favoured when CO binds through the C-end (cf. Fig. 9.4.9.1).
e/
However, in some exceptional cases, e.g. [(1l5-Cp)(OC)2W-C - Q-AIPh 3 ], CO has been suggested
to use the O-end for bridging. In the said example, coordination through the O-end occurs to Al which
t.m
fails to participate in n-back bonding. Formation of unstable isocarbonyl(carbonyl)gold, i.e. [COAuCO]

(a linkage isomer of bis(carbonyl)gold, [AU(CO)2]) has been suggested to occur due to the coordination
of one CO molecule through the O-end. This conclusion has been made from the spectroscopic data.
Condensation of gold with excess CO in a noble gas matrix (matrix isolation) at very low temperature
e
produces the isocarbonyl gold. Here it may be mentioned that the enhanced electronegativity of gold
er
(in fact, among the metals, gold shows the highest electron affinity) disfavours the metal ~ CO
n-bonding which is the most important factor to determine the stability of metal carbonyls. Thus gold
H
is reluctant to stabilize the Au-CO bond through the x-back bonding. In such cases, bonding
through the O-end may be relevant only to some extent. Because of the increased number of low
k
shielding d- and f-electrons in the heavier transition metals, z* (i.e. effective nuclear charge) increases
lic
and it disfavours the back donation of electron from the metal centre. Thus, in general, the heavier
congeners and late members of the transition series form the relatively unstable carbonyls because of
C
:Co: Ligand - Coordination by C-end vs. O-end

• The lone pair on each end basically resides in a respective nonbonding MO.
• The NBMO housing the C-Ione pair is basically enriched in p-character while the NBMO
housing the O-lone pair is enriched in s-character. This favours the donation of the C-Ione pair.
It is also favoured due to the less electronegativity of C.
• The n* -MO to participate in the metal ~ ligand n-backing is predominant in the character of
C-orbitals. This favours the M ~ C n-bonding over the M ~ 0 1t-back bonding.
the disfavour in n-back bonding. (cf. stability of carbonyl halides: [Ni(CO)3X]- vs. [Ni(CO)4];
[Pt(CO)zX z] vs. [Pt(CO)4], Sec. 9.4.18)
9.4.7 Preparation of Metal Carbonyls, Carbonyl Halides, Carbonyl Hydrides and

Carbonylates
(A) Direct synthesis: CO can directly react with the finely divided powders of metals under high
ry
pressure and at high temperature to produce the respective metal carbonyl. However, for nickel, no such
drastic condition is required.
ra
Ni (s) + 4CO (g) ~ [Ni(CO)4] (I), (30°C, I atm, i.e. mild condition).
[Ni(CO)4] formed in the above reaction decomposes at a higher temperature to release the Ni-metal.
ib
These reactions are utilized to extract and purify nickel in Mond's process.
yl
Fe (s) + 5CO (g) ~ [Fe(CO)s] (I), (liquid at room temperature), (200°C, 200 atm)
2Co (s) + 8CO (g) ~ [Coz(CO)s] (s) (solid at room temperature), (150°C, 35 atm)
m
[Cr(CO)6] and [MO(CO)6] are also prepared in this way.
Many unstable carbonyls formed by the early members like Ti (i.e. [Ti(CO)6]) failing to satisfy the
he
18e rule and late members or heavy congeners like Pd, Pt, Ag, Au, etc. disfavouring the back-bonding
(due to the increased effective nuclear charge and electronegativity) can be synthesized in this route.
lc
Synthesis of such unstable carbonyls, e.g. [Ti(CO)6]' [Pd(CO)4], [Ag z(CO)6], [CUZ(CO)6], [Pt(CO)4],
[Au(CO)z], [(CO)Au(CO)] i.e. isocarbonyl(carbonyl)gold etc. in this route is generally carried out by
ea
the action of CO on metal atoms at very low temperatures in a rare gas matrix (known as matrix
isolation).
th
(B) Reductive carbonylation: Reduction of metal compounds (generally halides) in presence of CO

e/
(generally under at. high pressure, ca. 200-300 atm) produces the metal carbonyls.
In some cases, CO may itself act as a reducing agent. This advantage (i. e. no requirement of external
t.m
reducing agent) is available generally for the metal oxides used as the starting material.
e
OS04 + 9CO -3-~~-0:-~~) [Os(CO)s] + 4CO z

er
In general, external reducing agents (e.g. Hz, Na, AI, Mg, Cu, LiAIH4, trialkyl alumnium, etc.) are
used. It is illustrated in the following examples.
H
VCl 3 + 4Na + 6CO (200 atm) d::~~e) [Na(diglyme)z]+ [V(CO)6] -

k
/ \0/ \OMe
lic
diglyme = MeO i.e. di(2-methoxyethyl)ether

C
AICl 3 in C 6 H 6 [ ( ) ]
CrCl 3 + Al + 6CO ----~) , Cr CO 6 + AICI 3
!
(in solution phase)
CrCl 3 + 6CO ether, LiAIH 4 ) [Cr(CO )6]

I ISoC, 70 atm
AIEt)
2[Mn(acac)3] + lOCO --~) [M~(CO)IO] + oxidation product of AIEt3
AIEt)
Mo0 3 + 6CO ) [MO(CO)6] + oxidation product of AIEt3
diglyme, Ph 2CO
2MnCl 2 + 4Na + lOCO ) [Mn2(CO)IO] + 4NaCI
ry
6RuCl 3 + 9Zn + 24CO -7 2[Ru3(CO)12] + 9ZnCl 2
(Note: Generally, the temperature and pressure required for the synthesis of carbonyls through the
ra
reductive carbonylation are less than those required for the direct combination of CO).
(C) Thermolysis and photolysis: Polynuclear carbonyls may be obtained from the thermolysis and
ib
photolysis of carbonyls of lower nuclearity.
yl
2[Fe(CO)5] ~ [Fe2(CO)9] + CO
m
?[Fe2(CO)9] ~ 2[Fe3(CO)12] + 3CO
he
3[OS(CO)5] ~ [OS3(CO)I2] + 3CO
In these reactions, the.M-CO bonds are broken and to maintain the 18e rule, the M-l\1 bonds are
produced. Thus CO are released.
lc
ea
(D) Nucleophilic attack by carbonylate anion on the carbonylate cation: It leads to the dinuclear
carbonyls. Carbonylate anions being soft prefer the soft carbonylate cations.
[Re(CO)s]- + [MnBr(CO)s] ~ [(OC)sRe-Mn(CO)s] + Br- )
th
.
[CoCCO) ]- + [MnBr(CO) ] ~ [(OC) Co-Mn(CO) ] + Br- SynthesIs ofhetero-
e/
4 . S 4 S nuclear carbonyls
[(CO(CO)4]- may be obtained as Na[Co(CO)4])
t.m
Note: Carbonylate anions being soft may also combine with the other soft acids like Hg 2+.
2[CO(CO)4]- + Hg 2+ -7 [(OC)4Co-Hg-Co(CO)4].
• [CO(CO)4]- may be obtained through the reduction of [C0 2(CO)8] by alkali metals like Na in a
e
chelating solvent like diglyme.

er
[C0 2(CO)8] + 2Na diglyme ) 2[Na(diglyme)x][Co(CO)4] i.e. 2Na[Co(CO)4].

H
(E) Synthesis of carbonyl hydrides and carbonylate anions through the reduction of metal carbonyls
(cf. Sec. 9.4.17): Some representative examples are given below:
k
Hg + [C0 2(CO)8] ~ Hg[CO(CO)4]2

lic
[C0 2(CO)8] + 2Na diglymesolvent) 2NILC~(CO)4]; Na[Co(CO)4] + HCI-7 NaCI + [HCO(CO)4]

C
liq. NH) solvent

[Fe(CO)5] + 2Na ) Na2[Fe(CO)4] + CO; Na2[Fe(CO)4] + 2HCI-7 2NaCI + [H2Fe(CO)4]
THF solvent
[Cr(CO)6] + NalHg ) Na2[Cr(CO)5] + CO; Na2[Cr(CO)5] + 2HCI + 2NaCI + [H 2Cr(CO)5]
[Mn 2(CO)IO]+2Li THF) 2Li[Mn(CO)s]; Li[Mn(CO)5] + HCI-7 LiCI + [HMn(CO)5]
[Mn 2(CO) 10] + 2KH THF solvent) 2K[Mn(CO)5] + H2;K[Mn(CO)5] + HCI -7 KCI + [HMn(CO)5].
In presence of a strong Lewis base like RNC, py or PPh3, [C0 2(CO)8] undergoes disproportionation
to produce the carbonylate anion.
[C0 2(CO)8] + 5CNR ~ [Co(CNR)s]+[CO(CO)4]- + 4CO
[C0 2(CO)8] + 2PPh3 ~ [Co(CO)3(PPh 3)2]+[Co(CO)4]- + CO

In presence of OH-, [Fe(CO)s] produces [HFe(CO)4]-
o +2 +4-2
[Fe(CO)s]+20H- ~HC03 + [HFe(CO)4]-
ry
r ~:~2n~~) )[Fe 3(CO)12] _~~~, )[Fe 3(CO)" ]2- ~[HFe3 (CO)II r
ra
[HFe(CO)4
The probable mechanistic path of disproportionation of [Fe(CO)s] involves the fJ-elimination.
ib
yl
~I 0-0H
m
/ IFe-C_O+
U ..
(Nucleophilic attack)
he
~ p-eliminalion
lc
ea
th
e/
Note: The above reaction mechanism is quite important in connection with the water gas shift reaction
(WGSR) i.e. H 20 + CO ~ CO 2 + H 2.
t.m
Note: Carbonylate anions can act as the nucleophiles and Bronsted bases. On protonation of the
carbonylate anions, the carbonyl hydrides are produced. The carbonyl hydrides can act as the Bronsted
acids. However, these properties depend on the nature of metal centre. [V(CO)6]-' [CO(CO)4]-
[Re(CO)5]-, [HOS(CO)4]- are the very weak bases; [Mn(CO)s]- and [HFe(CO)4]- are the weak bases;
e
[Fe(CO)4]2- is a strong base. The pKa-values of their corresponding conjugate acids are given below.
er
[H 2Fe(CO)4] (pKal = 4.4, pKa2 = 14.0); [HMn(CO)s] (pK{/ = 7); [HRe(CO)s] (pKa = 13.5);
[HMo(CO)s] (pKa = 7.5), [HCO(CO)4] (pKa = 1.0), [HV(CO)6] is also a fairly strong acid.
H
The Bronsted acidity of the carbonyl hydrides depends largely on the relative stabilities of the
k
conjugate bases like [CO(CO)4]-' [V(CO)6]-' etc. These are stabilised by the charge delocalisation
through the n-aeidie property of the CO ligands. Obviously, replacement of CO by a weaker 1t-acid
lic
ligand like PPh 3 will reduce the acid strength (ef [HCO(CO)4] (pKa ~ 1.0), [HCo(CO)3(PPh 3 )]
(pKa ~ 7.0). These aspects have been discussed in Sec. 10.1. Metal to CO 1t-back bonding is relatively
C
disfavoured for the heavier congeners because of the increased effective nuclear charge and
electronegativity. It makes [Re(CO)s]- a stronger base than [Mn(CO)s]- (i.e. [HMn(CO)s] is a stronger
acid than [HRe(CO)s]).
Carbonyl hydrides may be prepared also in the following reactions.
1
Co+4CO+ -H')
2 -
Relationship between carbonyl and carbonyl hydride/carbonylate

In terms of electron count, the 2e donor CO may be replaced by (i) 2e electrons, (ii) by a hydride
(H-), (iii) 2 hydrogen atoms. This is illustrated below:
[Fe(CO)s] : [Fe(CO)4]2-, [Fe(CO)4H]-, [Fe(CO)4H2]
[Fe2(CO)9] : [Fe2(CO)RJ2-, [Fe2(CO)gH]-, [Fe2(CO)8H 2]
ry
[Co2(CO)s] : [C0 2(CO)7]2-, [C02(CO)7H]-, [C02(CO)7H2], [CO(CO)4]-' [CO(CO)3]3-
[Cr(CO)6] : [Cr(CO)6]' [Cr(CO)s]2-, [Cr(CO).i]4-
ra
(F) Synthesis of metal carbonyl halides through the oxidation of metal carbonyls (cf. Sec. 9.4.18):
ib
When the metal carbonyls are oxidized by halogens, in some cases, metal carbonyl halides are produced.
[Mn2(CO)IO] + X 2 ~ 2[Mn(CO)sX], (X = CI, Br).
yl
[Fe(CO)s] + Br2 ~ [FeBr2(CO)4] + CO; Fel2 + 4CO ~ [Fe(CO)4I2]
m
2PtCl 2 + 2CO ~ [Pt(CO)CI 2]2; 2[MnBr(CO)s] ~ [MnBr(CO)4]2 + 2CO
AuCI + CO
he
C2Cl 4 solution >[Au(CO)CI ]
3 200°C, pressure 3
lc
ea
+2PPh 3
IrCI 3·xH?O + L ~ [Ir(CO)2CI(L)] -CO
) [Ir(CO)CI(PPh 3 )2(L)]
- L = p-toludine.
cl-L
th
o
75
Vaska's Complex
e/
N a 2 [IrCI 6 ] -(e-th-:~e"';';""3:-'~-l~-CO-l)~) trans - [Ir(CO)(CI)(PPh 3 )2 ](Vaska's Complex)

t.m
e
er
H
[M(CO)4X]2: (M = Mn, Re; X = Br, I) (M =Rh)

k
co
lic
OC I / CO
"RU
C
co F /I~ F
oc'" 1/ 1
OC I/F F F"I/CO
M "
/RU"", / I""'-
Ru
OC/ "'II oc I F F /F CO CO
co CO ~I/ Ru
[M(CO)412]'
M = Fe, Ru
oc/I ~co
CO
[RU(CO)3 F2]4
py
CO
OC"", I/ PY +2py
OC"", I/ py
+2py
--~~~ 2 Mn ~ 2 Mn
OC/ I ""'I
-2CO
I
OC/ CO""'I
ry
CO
ra
Fig. 9.4.7.1 Structures of some representative carbonylhalides.
Vaska's compound is obtained in the reaction of sodium hexachloridoiridate(IV) with triphenyl-
ib
phosphine in ethylene glycol under an atmosphere of CO. The compound can participate in different
types of addition reaction (ef addition of H 2, O 2 , HCI, RX, etc.)
yl
The dimeric carbonyl halides are bridged by the halogen (Fig. 9.4.7.1). These dimers cleave in
m
presence of suitable ligands like py, RNC, etc. to give the monomeric species.
(G) Synthesis of metal carbonyl alkyls: In the M-R a-bond, there is no 1t-bond and the transition
he
metal alkyls are extremely unstable. However, the metal-alkyl bonds may be stabilized by the pres-
ence of strong a-donor ligands and 1t-acid ligands. In fact, such metal carbonyl alkyls are stable and
these are prepared from the carbonylate anions.
RX + Na+[Mn(CO)5]- ~
lc
NaX + [R-Mn(CO)s]
ea
RCOCI + Na+[Mn(CO>sr ~ NaCl +[R-~-Mn(CO)5]
th
e/
1~,-co
t.m
[R-Mn(CO)s]
In the above reactions, carbonylate anions attack as the nucleophiles on the carbocationic carbon.
e
[HCO(CO)4] can react with the olefins to introduce the Co-C bond.
r
er
[HCO(CO)4] + RCH= CH 2 ~[ O(CO)4l

H
R-CHCH 3 J
k
This reaction is important in connection with the homogeneous catalysis (cf Sec. 10.3.4).
lic
9.4.8 Reactivities and Mechanistic Aspects of Metal Carbonyls and Carbonylates

C
These aspects have been discussed in detail in Chapter 10.
9.4.9 Bonding in Carbonyls with Special Reference to the Linear M-C-O Groups
and J..I.2-CO group
(a) VBT treatment: In terms of VBT, the structure and bonding in the mononuclear carbonyls are as
follows:
(i) [M(CO)6]: octahedral e.g. [V(CO)6]' [Cr(CO)6]' etc.; d?sp3 hybridization at the metal centre.
(ii) [M(CO)5]: trigonal bipyramid; e.g. [Fe(CO)51]; dsp3 hybridization at the metal centre.
(iii) [M(CO)4]: tetrahedral, e.g. [Ni(CO)4]; Sp3 hybridization at the metal centre.
In all cases, the inner orbital complexes (i. e. low-spin complexes in terms of CF!) are formed by
using the (n - l)d orbitals in hybridization. To provide the necessary (n - l)d-orbitals (i~e., d X 2 -y 2 and d z2
for octahedral; d Z2 for trigonal bipyramidal), the electrons are properly arranged· w~thin the inner
d-orbitals. It is illustrated below. .
ry
3d 4s 4p
[V(CO)6]: .~
~
ra
(17e)
t t t t t t
ib
L L
l )
~ (L=CO)
2
d sp3
yl
[Fe(CO)s]:
B EEEJ
m
(18e)
t t t t t
he
)
lc
B
ea
[Ni(CO)4]:
(18e)
t
th
e/
3
sp
t.m
The ligand ~ metal dative a-bonding can thus be rationalized. The Lewis basicity of CO is very
poor. To explain the stability of metal carbonyls, multiple nature of the M-CO bond is to be considered .
in terms of the following resonating structures.
e
·-·rr ('+
er
M-C_O:" ~ M=C=O
The n-bonding thus helps to remove the accumulation of negative charge on the metal centre. In fact,
H
accumulation of negative charge on the metal centre is not energetically favourable.

(b) MOT treatment: The bonding in metal carbonyls can be better explained in terms of MOT. For
k
this purpose, it is required to recapitulate the molecular orbital picture of CO (Fig. 9.4.9.1). CO is
lic
bearing two lone pairs housed in the nonbonding MOs. The lone pair on C is residing in a NBMO
predominantly enriched with the p-orbital character of carbon. It may be noted that this NBMO is
C
also the HOMO. The other lone pair residing on 0 is also housed in a NBMO predominantly enriched
with the 2s-character of oxygen, i.e. the C-Ione pair is of higher energy compared to the O-lone pair;
in fact, the C-Ione pair resides in a HOMO while the O-lone pair resides in a low energy MO. Besides this,
oxygen is more electronegative than carbon. Thus the lone pair residing on the C-atom is more suitable
compared to the lone pair residing on the O-end for a-donation because of the following reasons.
• Lone pair on C: HOMO in nature; (cf. the lone pair on the O-end is not in the HOMO; rather it
is lying in a low energy inner NBMO enriched with the 2s-orbital character of oxygen).
• Lone pair on C: less s-character in the NBMO acting as the HOMO;
• Lone pair on C: residing on the less electronegative atom.
• In reality, the poor a-basicity of CO is synergistically enhanced by the metal ~ LUMO (n*)
n-back bonding; the said LUMO (n*) is predominantly localized on the C-end; i.e. the larger lobes
of the n*-MO are concentrated on the C-end and the smaller lobes are concentrated on the O-end.
Thus the n-back bonding (key factor to stabilize the adduct) is more favoured when CO binds
through the C-end; in fact, the O-end is not only a poorer a-donor but also a poorer
x-acceptor because only the minor lobes of the n*-LUMO are concentrated on the O-end.
ry
Nature of HOMO and LUMO of CO: Effect of a- and x-bonding
ra
on the C-O bond order in the metal carbonyls
ib
• HOMO: We have already mentioned that the HOMO is practically nonbonding but a careful
analysis shows that it is weakly antibonding between C and O. Thus it is reasonable that the
yl
a-donation from the HOMO will slightly increase the C-O bond order. This expectation has
been experimentally verified from the analysis of the unstable species like [Ag(CO)]+ having
m
the C-O bond length 107.7 pm (ef C-O bond length in free CO = 112.8 pm). It should be
mentioned that the slight strengthening of the c-o bond due to the a-donation from the
he
HOMO is only noticeable when the metal ~ CO back bonding is insignificant as in the
case of Ag+, Au+, etc. Because, the said back bonding with the LUMO (which is a n*-MO)
lc
will weaken the C-O bond. The weak n-donor property of Ag+, Au+, etc. is due to their high
ea
effective nuclear charge «(f the effect of low shielding inner d- and I-electrons).
• LUMO: This is strongly antibonding between C and O. Thus acceptance of electrons in the
LUMO through the n-back bonding will reduce the C-O bond order. This aspect is well
th
documented and experimentally verified.

e/
• Resultant effect on the C-O bond order: The metal f- CO a- donation involving the
HOMO (which is weakly antibonding in nature) slightly enhances the C-O bond order
t.m
while the metal ~ CO n-back bonding involving the LUMO (which is strongly antibonding
in nature) significantly reduces the C-O bond order. Thus in most of the stable carbonyls
where n-bonding is quite efficient, the C-O bond order decreases compared to that of free CO.
e
er
Factors disfavouring bonding through the O-end of CO in carbonyls

The a-bonding is favoured through the C-end. The reasons behind this has been already explained
H
(Sec. 9.4.6). The Lewis basicity of CO is negligible to stabilize the adduct. Stability of the adduct
is earned through the n-back bonding. The a-donation and n-acceptance work in a synergistic
k
fashion. In absence of the x-acceptance, the a-bonding, i.e. a-basicity is too weak to stabilize
lic
the adduct. In fact, this is why, CO fails to form an adduct with the main group elements incapable
of forming the n-back bonding. Thus, the n-bonding is the main driving force for the stability of
C
the adduct and this n-back bonding is favoured when CO makes the a-bond through the C-end. If
it makes the a-bond through the O-end, then x-back bonding becomes inefficient because the
involved LUMO (i.e. 1£*) is predominantly localized on the C-end not on the O-end. In fact,
the O-end is not only a poorer a-donor but also a poorer x-acceptor «(f Sec. 9.4.6).
The poorer a-donor property of the O-end is due to the low energy of the NBMO (basically the
0-25 orbital) housing the O-lone pair and the higher electronegativity of 0 and the poorer
n-acceptance of the O-end is due to the concentration of only the minor lobes of the n*-LUMO on
the O-end. Probably, the unstable isocarbonyl(carbonyl)gold [(CO)Au(CO)] involves the ligation
of one CO through the O-end (cf. Sec. 9.4.6). The probable reason has been discussed in Sec. 9.4.6.
(LUMO)}
,~,
a*
/ Enriched with
2p
~- - -:=::==,'" "','
I I~,
(-10.7 eV) \ ''-
\ ,
...,'Ilr_~
j"'....
a nb ')
Ii
X
,\+
t,
\'
(HOMO)
the 2p-orbital
character of C
2p
\,
" \jI
(),\~"
sp 2 ( , .~ ) ~ c::::==_ - -
~
" ~ ..,"" '"
ry
\
, ~' ~
.
'r-------"'''',' (-16 eV)

2 I,. ( ) \ I ' 1
~,. \jI SP1 \ ,'I'(SP)2' 1
ra
------w- \ " 1
\ " 1
(-19.5eV) "
," ~" "
ib
\
\ a , "
\ .J , "
\ ., I C
\~ I,
yl
1\
I,
Enriched I,
m
with the 25 a nb ~ 1 ,
orbitalof~O ~---~ ~
'JI (SP)1 " ,
he
" 2s
~
(-32.4 eV)
1s
-------~..,
,
..,..,,~,
a*
lc ,,
ea
Pure
", ~ :)------+---Pure
Hybridised '--rv---"'''' Hybridised
____ l -...,.- J
th
~-----J
(C)AOs (CO) MOs (O)AOs

e/
(a)
t.m
1
1
rf:\i i
",,~
e
LUMO .. It' :(7

o
er
------ C--------O-----
Qj
i:
H
~:
-----
Enriched with the character : :
k
of 2p orbital of C ~: : ¥' Enriched with the character

_____ ~~ G>- - J:::'. ~8 ~f 25 orbital of 0
lic
'JI(sp) 2 I "-I
~I '-.:/1
1 'JI(sp) 1 (NBMO)
C
: (Lone Pairs) ~
HOMO (NBMO) u: a
nb
.' /' Enriched with the character of
+ ¥ 2p orbital of 0
1t
----~~--- It-BMO
1 1
1 1
1 1
(b)
cr*
I
\
'I \
, I
\
, /1 \
,,
I 1t* \
I \
, , I
I,.
,. \ \
,, ,. ,.
\
2p ,.( LUMO \
\ \
I \ \
"
ry
\ \
(-10.7 eV)
\':
\ " I
\
\
\
\
\
~ 0( \
I , \ \
ra
\\ \
\\ I " ,, crnb \
\
\
\
1~
\\1
,,
\'1
.... .... \ \
.... .... \ \
~\ HOMO .... ....
ib
\\
1\\ I .... .... \ 2p
I \\ ' .... ....\ \\
1
" :1: ....;.~
UJ
yl
I , \ \ 'I
I , \\ 'I (-16 eV)
I, \\ ' I
~
m
6 \ \ ' I
'I
\ \ \ 'I
\ \ \
(-19.5 eV) \ \ \
, , , " II
,,
he
\ \ \ I
(AOs of C) \ \ I
\
\
\ \
\ \ ,, I
I
, ,,
\ I
\
\ \ 1t b
\ I
\
\
\
\
\ n 1l lc I
I
I
\ \ I
ea
\ \ I
\\ cr I
1~
\t J
crnb 2s
- - - - - - - - ----it:-1~- -
th
---'tI1~~--
(-32.4 eV)
MOs.of CO (AOs of 0)
e/
(c)
t.m
Fig. 9.4.9.1 (see Vol. 2 for details) (a) MO energy level diagram of CO, (b) Shapes of the MOs of CO, (c) Approximate
molecular orbital diagram of CO. (Note: This diagram (c) can be approximately applied for the other heteronuclear
diatomic molecules like NO). 0'1,2,3 = c1'V2sC C ) + c2 'V2Px (C) + c3'V2px (0) (x-axis as the molecular axis); 01,2,3 denotes
e
0, O' nb and 0'*. 2s-orbital of oxygen is excluded from this process due to the large mismatch in energy.
er
Here it is worth mentioning that in the carbonyls, oxidation states of the metals are very low. Thus
if, only a-donation by the ligands occurs, then the metal will have to bear an accumulation of high negative
H
charges. Such an unfavourable condition can hardly be tolerated by the metal centre. But, in fact, to
remove this excess negative charge, the back bonding mechanism operates. The metal d-electrons
k
are pushed into the vacant n* -MOs of CO. These n* -MOs are the LUMOs predominantly enriched with
lic
the character of 2p atomic orbitals of carbon. The a-donation from the C-end and 7t-acceptance into
the vacant 7t*-MO predominantly residing on the C-atom work in a synergistic way.
C
In an octahedral geometry, the t 2g d-orbitals, i.e. dxy , d yz and dzx are suitable for the metal~ligand
back bonding. In a tetrahedral geometry, the e-set, i.e. d x 2 -y 2 and d z2 orbitals are suitable for the said
n-back ~onding. In an octahedral geometry, the three d-orbitals are equally probable for the n-back
bonding interaction with the six CO ligands while in a tetrahedral geometry, the two d-orbitals participate
in the n-back bonding with the four CO groups. Thus in both cases, the n-bond order becomes about
and the total bond order in each 'M-C' bond becomes l ( = lcr + !1t). Thus bondings in the
!
2 2 2
M-C linkage are:
ORGANOMETALLICS AND METAL CARBONYLS: X-ACID METAL COMPLEXES 1323
(i) ligand ~ metal, C-Ione pair ~ vacant cflSp3 (Oh)

C-Ione pair ~ vacant Sp3 (Td )
(ii) metal ~ ligand, metal t2g ~ vacant 1[* of CO (Oh)

metal e ~ vacant 1[* of CO (Td )
ry
The bonding scheme is schematically represented in Fig. 9.4.9.2
ra
Acceptor orbital of metal
ib
~+.C=O:--+
yl
==0
m
t HOMO
cr (M ~ CO)
he
(a) Sigma bonding in a terminal metal carbonyl linkage
Donor orbital of metal

lc
ea
th
e/
t.m
(b) Pi-bonding in a terminal metal carbonyl linkage, 1t (M ~ CO) (cf. Fig. 9.4.11.5)
e
er
Fig. 9.4.9.2 Schematic representation of synergistic 0- and x-bonding in a terminal metal carbonyl bond.
(c) Overlap interaction for the bridging 1l2-CO groups: For placing a Jl2-CO group along a
H
M-M bond, we need the consideration of formation of the multi-centred MOs. The donation of the
lone pair from the C-end of CO can occur to the metal d-orbital. The filled d-orbitals of the metal
k
centres can participate in the 1t-back bonding with the vacant 1[*-MO of CO. There is an extensive
lic
delocalization of the electron in the M- C -M moiety by involving the d-orbitals of the metal centres.
For this delocalization of the electron in the M- C -M moiety, the bond angle is found to be close
C
to 90° (cf. C-C -C ::::: 120° in the saturated ketones where no such electron delocalization occurs).
Thus, it is evident that the bonding mechanism of a Jl2-CO along a M-M segment is very much similar
to that of a linear M-C-O segment (i.e. terminal CO group). The overlap interaction of a bridging
Jl2-CO is schematically represented in Fig. 9.4.9.3.
In terms of VBT, the C-centre of the bridging CO group is approximately sp2-hybridized. Two
appro~imate sp2-hybrid orbitals
(predominantly enriched with the p-character indicated by the
M- C -M angle close to 90° carrying the unpaired electrons are projected towards the metal
centres.
o
III
~
c IIIc
ry
ra
ib
yl
m
he
c
IIIo lc
ea
(a)
th
s-p hybrid orbital

e/
~
{"'-/ (enriched with the p-orbital),
+ + each bearing an unpaired
t.m
• • electron.
Mo ==========~M
e
er
H
(c) (d)
Fig. 9.4.9.3 (a) and (b) In terms of MO-picture of CO. Overlap interaction of HOMO (a) and LUMO (b) of the bridging
k
CO-group with the metal d-orbital. (c) In terms of VBT model, overlap interaction of the bridging CO-group with the
lic
metal d-orbitals. (d) Nearly linear bridging CO group in [(llS-Cp)Mo(CO)2]2 (see Fig. 12.1.17.1 for details).
C
9.4.10 Evidences in Favour of 7t-Back Bonding (~etrobonding)in Metal Carbonyls

(i) Nonexistence of [Zn(CO)4]2+: Ni(O) and Zn(ll) are the isoelectronic species (3d lO system).
Ni(O) fonus the stable tetracarbonyl, [Ni(CO)4] while Zn(ll) fails to form the similar carbonyl, i.e.
[Zn(CO)4]2+. Zn(ll) being dipositive acts better as a Lewis acid compared to neutral Ni(O). Thus,
a-donation towards Zn(ll) by CO is expected to be more efficient compared to the case of Ni(O).
If this a-bonding were primarily important to determine the overalls stability of the carbonyl
complex then [Zn(CO)4]2+ would be more stable than [Ni(CO)4]. But, [Zn(CO)4]2+ does not
exist. It indicates the importance of n-bonding to stabilize the metal carbonyl adduct. In the
elusive compound [Zn(CO)4j2+, the n-back bonding Zn(ll) ~ n*(CO) is less favoured because of
the positive charge on the metal centre. On the other hand, in the n-back bonding, Ni(O) ~
n*(CO), no such disfavour occurs.
Thus, the n-bonding is less efficient in [Zn(CO)4]2+ compared to that in [Ni(CO)4] because the
dipositive Zn(II) is much more reluctant than neutral Ni(O) to donate the d-electron to the ligand.
Lack of an efficient 1t-back bonding (i.e. retrobonding) in [Zn(CO)4]2+ makes the species
nonexistent.
ry
In general, the stable carbonyls are formed with the metals in low oxidation states like 0, -1, + 1
for which metal ~ ligand n-back bonding is not electrostatically hindered.
ra
(ii) No stable adduct of CO with the main group metals: The main group metals lack in suitable
nonbonding valence electrons for the metal ~ CO n-back bonding. This is why, they fail to form
ib
the adduct with CO.
yl
Stability of the H3 B ~ CO adduct
m
In fact, because of the absence of n-back bonding (i.e. retrobonding), the main group elements, in
he
general, fail to make any stable adduct with CO. The adduct, H 3B f - CO is an exceptional one in
this regard. It has been argued that its stability is earned through the hyperconjugation which has
been already discussed (see Ch. 15, Vol. 3). But, the v eo value (= 2165 cm- I , cf. veo = 2143 cm- I
lc
for free CO) found in the adduct indicates the insignificant contribution of hyperconjugation.
ea
(iii) Relatively less stable carbonyls formed by the heavier congeners and late members of the
transition series (ef Sec. 9.4.12): For the d-block elements, electronegativity increases along the
th
series and along the group from top to bottom (see Chaper 8, Vol. 1). Thus, the late members of
e/
a particular series and heavier congeners are relatively more electronegative (i.e. d-electrons are
more tightly bound). Obviously, the members at the bottom of the right corner of the d-block
t.m
elelnents are of very high electronegativity. Such members are expected to be reluctant in making
the metal ~ CO n-back bonding. Thus, such carbonyls, if at all formed, will be only marginally
stable. In fact, this prediction has been experimentally realized. The very unstable carbonyl species,
[Ag(CO)][B(OTeFs)4] shows v eo = 2204 cm- l (cj~ veo ::; 2143 cm- I for free CO) indicating
e
practically no n-bonding. A similar situation arises for the unstable species [Au(CO)CI] having
er
veo = 2152 cm- I ) 2143 cm- I of free CO and in [Pt(CO)4]2+ (veo = 2251cm- 1 ) 2143 cm- I ).
In fact, stability of the metal carbonyls is directly correlated with the efficiency of n-back
H
bonding which is very often measured in terms of Yeo. This aspect will be discussed later in detail.
• Relative stability order [Ni(CO)4] » [Pd(CO)4] » [Pt(CO)4] (transient): This stability sequence
k
can be explained by considering the relative ease of metal ~ CO n-back bonding sequence: Ni
lic
~ CO ) ) Pd ~ CO ) ) Pt ~ CO (ef stability order: [Ni(CO)4] » [Ni(COhX]-) [Ni(CO)2X2r~

but [Pt(CO)2X2], [Pt(CO)3X]+» [Pt(CO)4]; Sec. 9.4.18 for explanation).
C
Note: For the unstable species like [Ag(CO)][B(OTeFs)4]' [Au(CO)CI], etc., the n-bonding has
practically no role. Here the marginal stability arises from the a-donation from CO. This
a-donation is relatively favoured for the electron withdrawing halide and positive oxidation state
of the metal as in [Ag(CO)]+ and [Au(CO)CI]. A careful analysis of the MO diagram of CO
indicates that, the HOMO used for a-donation is weakly antibonding in character. Thus the
a-donation slightly increases the C-O bond order and consequently vco also slightly increases
compared to that of free CO. The effect metal f - CO a-donation on v eo is noticeable only when
the n-back bonding involving the strongly antibonding LUMO of CO is practically absent be-
cause the said n-back bonding can overweigh the effect of a-bonding on vco.
(iv) Double bonded character in the metal-carbon bond: Because of the n-back bonding, the metal-
carbon bond is expected to have some double bonded character. Acceptance of electrons in the
n*-MO of CO produces two effects:
• Strengthening of the M-C bond, i.e. partial double bonded character in the M-C bond, i.e.
increasing the VM-C stretching frequency.
• Weakening of the c-o bond, i.e. lowering of the bond order in the C-O linkage, i.e. decreasing
ry
the vc- o stretching frequency.
ra
In fact, in free CO, the carbon-oxygen bond length is 113 pm, while in most of the metal carbonyls
it is - 115 pm. This slight increase in the bond length is definitely in the expected direction. But
ib
this slight difference very often lies within the experimental uncertainties.
(a) • Bond length parameters in [Mo(CO)3(dien)] vs. [MO(CO)6]: [Mo(CO)3(dien») has been
yl
synthesized in a reaction between dien [diethylenetriamine, i.e. (H2N-CH2-CH2)2NH) and
m
[MO(CO)6). In the mixed ligand compound, [Mo(CO)3(dien»), dien acts as a tridentate ligand
through the Sp3 N-donor sites. The Sp3 N-donor sites act as the a-donor sites but cannot act as the
he
n-acceptor sites because of the absence of any suitable vacant orbital on the N-donor sites. Thus,
the three t 2g orbitals are involved in the n-back bonding with the three CO groups. On the other
lc
hand, in the parent carbonyl, i.e. [MO(CO)6]' the three t2g orbitals are involved in the n-back-
bonding with the six CO groups. Consequently, it is reasonable to expect that in [MO(CO)6l, the
ea
average n-bond order in each Mo-C linkage is half (112) while in [Mo(CO)3(dien») the average
n-bond order in each Mo-C linkage is unity. Here it is worth mentioning that the good a-donor
th
property of three sp3-N sites of dien enhances the negative charge on the metal centre and
it favours the M'~ CO n-back bonding further. Here it is worth mentioning that the
e/
noncompetitive n-bonding from the trans-positions in [M(CO)3(dien)] will also strengthen

M ~ CO n-back bonding (see Fig. 9.4.11.5). This aspect has been discussed in detail in Sec. 9.4.11.
t.m
Thus, the Mo-C bond of [Mo(CO)3(dien») is expected to be shorter than that in [MO(CO)6]' i.e.
bond length order: Mo-C in [Mo(CO)3(dien») ( Mo-C in [MO(CO)6] but C-O in
[Mo(CO)3(dien)]) ) C-O (in [MO(CO)6).
e
More favourable factors for M ~ CO n-bond-

ing in [M(CO)3 (dien)]
er
• Less number of competitive CO groups

H
(3 vs. 6).
• Good a-donor properties of dien.
• Absence of competitive interaction from the
k
trans-positions (el Fig. 9.4.11.5).

lic
The expectation and observation have been analyzed in another way. Because of the said n-back
C
bonding, it is reasonable to expect that the Mo--C bond length should be smaller than the sum
of the radii of the zero-valent Mo-atom and sp-hybridized C-atom, i.e. r(Mo--C)obsd ( r(Mo o) +
r(C-sp) = r(Mo--C)calcd. The calculated value considers the Mo--C single bond.
In fact, the prediction has been supported experimentally by considering the Mo--N bond where
there is no n-back bonding as follows:
r(Moo) = r(Mo--N)obsd - r(N-sp3)
= 232 pm - 70 pm = 162 pm
Here, in calculating the radius of zero-valent Mo, i.e. r(Mo o), the experimentally observed
Mo--N bond length has been considered as a pure single bond. In fact, Cotton (1965) estimated
the radius of zero-valent Mo in this way. The calculated Mo-C single bond length is obtained as
follows:
r(Mo-C)calcd = r(Mo o) + r(C-sp) = 162 pm + 70 pm
= 232 pm ) 194 pm = r(Mo-C)obsd'
(b) • Bond length parameters in [Cr(CO)3(dien)] vs. [Cr(CO)6]: A similar observation has been
ry
noted in the related compounds, [Cr(CO)6] and [Cr(CO)3(dien)].
(c) • Bond length parameters in [Cr(CO)s(PPh3)] vs. [Cr(CO)6]: [Cr(CO)5(PPh3)] and [Cr(CO)6]
ra
compounds may be analyzed in the same way. Ph3P is a good a-donor ligand and it is also a
1t-acid ligand but it is weaker compared to CO as a 1t-acid ligand. The two trans-n-acid ligands
ib
will compete for the same two t 2g orbitals for n-bonding. On the other hand, two cis-n-bonding
ligands compete through one metal d-orbital. Thus, a x-bonding ligand L can affect the
yl
x-bonding of its trans-CO group more than that of its cis-CO group (cf. Fig. 9.4.11.5). Now
m
let us consider the following two trans-axial segments.
Ph 3P-Cr-CO and OC-Cr-CO
he
The n-back bonding in the Cr-C linkage is better in the Ph3P-Cr-CO segment compared to
that in the OC-Cr-CO segment because in the Ph3P-Cr-CO segment, there is a weaker
lc
1t-bonding ligand at the trans- position of CO. Thus, it is quite reasonable that in [Cr(CO)5(PPh 3)],
the Cr-C bond trans to the Ph3P ligand is relatively shorter compared to the Cr-C bond of
ea
[Cr(CO)6] (cf Fig. 9.4.11.5). The experimental findings support the expectation. P(OPh)3 is a
better 1t-acid ligand than PPh3 and consequently for P(OPh)3' the Cr-C bond at the trans-
th
position will be longer and the C-O bond at the trans-position will be smaller compared to the
case of PPh3.
e/
Cr-C in [Cr(C0 6 )] ~ 191.5 pm

t.m
Cr - PPh 3 ~ 242.2 pm Cr - C (trans to P(OPh)3) ~ 186 pm

Cr - P(OPh)3 ~ 231 pm Cr - C (trans to PPh 3) ~ 184.5 pm
e
v co (trans) ( V CO(cis) C-Oin [Cr(CO)6J~114.0pm

er
(cf. Fig. 9.4.11.6) C - 0 (trans to P(OPh)3 ~ 113.6 pm

{
C - 0 (trans to PPh 3) ~ 115.4 pm
H
(v) Weakening of the carbon-oxygen bond in the carbonyl compounds: It has been already
k
mentioned that in the metal ~ CO a-bond formation, CO uses the roughly nonbonding electron
lic
pair and consequently, this a-bonding will not affect much the C-O bond order. The very weak
antibonding character of the HOMO used for the a-donation leads to increase the C-O bond order
C
slightly through the metal ~ CO a-donation. But this effect is quite negligible. In the metal ~
CO n-back bonding, the electrons are pushed into the vacant n*-MO of CO. Consequently, this
1t-back bonding will reduce the C-O bond order, i.e. the C-O bond will be elongated with the
increase of efficiency of the metal ~ CO n-back bonding in the carbonyls, and the stretching
frequency (v eo ) of the C-O bond will decrease. The shifting of veo from that of the free CO
molecule gives the measure of the extent of n-back bonding (ignoring the slight effect of
a-bonding).
The above expectation of shifting veo·in the metal carbonyls has been experimentally verified (cf
Sec. 9.4.11).
9.4.11 Infrared Spectroscopy of Metal Carbonyls (see Secs. 9.4.6, 12.1.11, 17)
The absorption peaks due to theC-O bond in the IR-region are quite informative regarding the structure
and bonding of metal carbonyls.
• Number of C-O absorption peaks can predict the geometry of the complex.
• Shifting of vco can predict the nature of bonding.
ry
• v eo of carbonyls covers generally the window of 17,000-22,000 cm- 1 and this window is not
involved by the bands of other organic groups. Consequently, it is very easy to identify the veo
ra
peaks in the given window.
• Position of VC~I: 2143. em-II (free .CO); } These values are for the neutral molecules.
ib
1850-2140 cm_ (termlna.ll -CO), See Sec. 9.4.6 and Figs. 9.4.9.2, 3 to
yl
1
1700-1850 cm (J..l2-CO ), understand the C-O bond order
1600-1720 cm- 1 (J..l3-CO)
m
(A) Number of peaks and geometry of the mononuclear complexes: The number of ir-active modes
he
of vibration can be obtained from the point group and symmetry of the molecule. The details of the
prediction of the number of veo peaks for a particular geometry are beyond the scope of the book. Here
we shall only give the results (see Secs. 12.1.11, 17). lc
ea
Table 9.4.11.1 Number of IR-active C-O stretching modes in some selected geometries of mononuclear
carbonyls
th
Complex Geometry Point Group IR-active modes Number of IR-bands

e/
[M(CO)6] Octahedral °h T lu
[M(CO)sL] Square pyramidal C 4v Al + E (+ AI) 2 or 3
t.m
cis-isomer 3 or 4
[M(CO)4L2]
} trans- isomer
C 2v
D 4h
AI + B I + B 2 (+ AI)
Eu 1
[M(CO)3L3] } fac-i~omer C 3v Al +E 2
e
mer-Isomer C 2v 2A I + B 2 3 or 2
er
[M(CO)4L2X2] } cis-isomer C 2v Al + 8 2 2
H
trans-isomer D 2h B lu
[M(COh] Square pyramid C 4v 2A I +E 3
k
[M(CO)s] Trigonal bipyramidal D 3h A~ + E' 2

lic
[M(CO)4L]
} L(axial) (TBP)
L(equatorial) (TBP)
C 3v
C 2v
2A I +E
2A I + B I + B 2
3 or 2
4
C
[M(CO)312] 2L(axial) (TBP) D 3h E'

[M(COhL2] 2L(axial + equatorial) (TBP) C s 2A'+A" 3
[M(CO)4] Tetrahedral Td Al + T 2 2*
* In many cases, only one v eo is observed.
• [M(CO)sL] (C4v ) => if 4 CO groups lie in the same plane, i.e. basal plane and these are related
by the C4 axis, 2 bands instead of 3 bands will be observed.
• cis-[M(CO)4L2] (C 2v) => if the trans-CO groups are colinear then 3 bands instead of 4 bands will
be observed.
• mer-[M(CO)3L3] (C 2v ) =:) if the trans-CO groups are colinear then 2 bands instead of 3 bands will
be observed.
• [M(CO)4L] (C 3v ) =:) if the 3 CO groups related by the C 3 axis lie in a plane (i.e. basal plane), 2
bands instead of 3 bands will be noted.
The number and intensity of the absorption bands depend largely on the local symmetry about
the metal to which the CO groups are attached. For this purpose, the true molecular symmetry is not so
ry
important. The number of CO-absorption bands is higher for the less symmetric carbonyls.
If the CO groups are not related with the centre of inversion (C i ) or three folds (C 3 ) or higher
ra
axis of symmetry, then for each CO group there will be a separate absorption band. Let us illus-
trate for the linear and bent OC-M-CO segment.
ib
Linear OC-M-CO group:
yl
.
m
Resultant
O-C-M-C-O
O-C-M-C-O
he
~ ~
---. ----.
Symmetric stretch
(IR-inactive) Asymmetric stretch
lc (IR-active)
ea
Bent OC-M-CO group (C 2 axis)
th
Resultant
c/MJ"
e/
// ~"'o
t.m
Symmetric stretch Asymmetric stretch

(IR active) (IR active)
e
The linear segment possesses C i and Coo and the symmetric stretch is IR-inactve but the asymmetric
stretch is IR active, i.e. only one mode of stretching is IR-active. The bent segment possesses the C 2
er
H
NUMBER OF IR-BANDS FOR CO STRETCHING IN THE

MONONUCLEAR METAL CARBONYLS
k
• If the CO groups are not related with the centre of inversion (Ci ) or a Cn (n ~ 3) axis of symmetry,
lic
then for each CO group there will be a sep'arate IR-absorption band.

• If the CO groups are related by Ci or Cn (n ~ 3), then there will be one IR-absorption band for the
C
CO groups.
• A bent OC-M-CO group (i.e. C2 axis) gives two IR-peaks (both the symmetric and
antisymmetric streches are IR-active).
• A linear OC-M-CO group gives one IR-peak (cf. symmetric strech is IR-inactive;
antisymmetric strech is IR-active).
• [M(CO)6]' trans-[M(CO)4L2], trans-[M(CO)2L 4] and linear species [M(CO)2] with the centre
of inversion show only one IR-band for CO stretching.
• mer-[M(CO)3L3], cis-[M(CO)2L4] and cis-[M(CO)4L2] which do not prossess a Cn-axis (n ~ 2)
give as many IR-bonds as there are CO ligands.
C4
c
a t
L
t~~j-7ro °t~j7ro
ry
--L------M '. c , M '
' , I~: I , 2
, / ' III~",,
,
t------
,
/ ,
co
I ,
ra
L-------- oc -------t------co
c (C 2) L (D 4h )
ib
a
yl
t t
m
,t~I;77 ,t~j-7/ ,t~j-7 ,t~j;77/
he
, M " M ' , M ' , M '
,
,
/ I~'
L-------(----
I
I "
"
/I~'
L-------(----
I
I '
'
L
,/I~'
, lc I
,
(
"
"
L
/I~'
(
I
I '
'
ea
I I I I
~ "'" t '
th
A 1 mode A 1 mode 8 1 mode 8 2 mode

e/
( (Inactive) _ _(_A_ct_iv_e_)_ _) (_---(A-c-ti-Ve-)-_ _ __

(A_c_tiv_e_) _-J)
V V
t.m
Symmetric stretch Asymmetric stretch
Fig. 9.4.11.1 Different possible modes of C-O stretching in cis-[M(CO)4L2J (Vacant positions occupied by 4 CO groups
are not shown)
e
axis of symmetry and here both the symmetric and asymmetric stretches are IR-active. For the
er
linear segment, L-M-CO, only the asymmetric stretching mode is IR-active.

(a) Illustration for cis-[M(CO)4L2]: Now let us consider the complex, cis-[M(CO)4L2] (C 2v symme-
H
try, by considering the ligands as points) in which there is one linear OC-M-CO segment and one
bent OC-M-CO segment. For these two segments, there are four C-O stretching vibrations. These
k
are: 2A b B) and B 2 (cf Fig. 9.4.11.1). Out of these 4-stretching vibrations, 3 vibrations, i.e. A b B) and
lic
B 2 become IR-active. These IR-active modes are: asymmetric stretch (B)) for the linear segment; both
symmetric (A)) and asymmetric (B 2) modes for the bent segment. But, if the trans-CO ligands are not
C
exactly colinear, then the symmetric stretching mode (AI) becomes also IR-active. In such cases, 4
bands will be noted.
(b) Illustration for trans-[M(CO)4L2]: If we consider the trans-isomer, i.e. trans-[M(CO)4L2], the
4CO groups are equivalent and they are related with the C4 symmetry axis. In other words, there are two
equivalent linear segments. This is why, it shows only one IR-absorption band for the C-O stretching.
It again supports the view of the thumb rule:
"more symmetric species show the fewer IR-active bands"
trans-[M(CO)4(PMe3)2] (D 4h symmetry): One ir-band for c-o stretching
cis-[M(CO)4(PMe3)2] (C 2v symmetry): Four ir-bands for C-O stretching
",,1/ ",,1/
[M(CO)6 ]: M (1 IR-bands) [M(CO)sL]: M (2IR-bands)
/1"" /1"" (1 + 1)
ry
(Oh)
ra
(6 CO groups are equivalent) (When 4 CO-groups at the basal plane are
related with the C4 symmetry to give 1 band)
ib
L
1/ 1/
yl
[M(CO)s]: - M (2IR-bands) [M(CO)4L]: - M (2IR-bands)
m
(1 + 1) (1 + 1)
I"" I""
he
(Three equatorial CO groups are related (Three equatorial CO groups are related
with the Cs symmetry to give 1 band) lc
with the Cs symmetry to give 1 band)
ea
L""I/
th
M (3IR-bands)
L / I"" (1 + 2)
e/
(C 2v )
t.m
(Bent OC-M-CO segment gives 2 bands)

(Trans-CO groups are colinear to give 1 band)
e
L
er
(1 - IR band) [M(COhL2 ] : - M
1/ (1 IR-band)
H
I""
L
k
(D sh )
lic
(4 CO groups are related with the C4 (Three CO groups are related with
symmetry to give 1 band) the Cs symmetry to give 1 band)
C
Fig. 9.4.11.2 Number of IR-bands for the CO group in different mononuclear carbonyls (vacant positions are occupied
by the CO groups).
(c) Illustration for [Fe(CO)s]: Existence of 2 IR-bands indicates its trigonal bipyramidal geometry
not square pyramidal geometry (Fig. 9.4.11.3a). The square pyramidal [M(CO)5l is expected to show
three IR-bands for the CO group (cf. Table 9.4.11.1).
(d) Illustration for [M(CO)4{P(OPh)3}2] (M =Cr, Mo): The cis-structure (C 2v ) can give maximum
4 IR bands in the CO stretching region while the trans structure (D4h ) will give one IR band for CO.
These are experimentally verified (Fig. 9.14.11.3b).
In fact, by considering the number of IR band in the CO stretching region, geometry of the complex
can be determined.
(B) Intensity of the bands: The general rule of thumb is:
more symmetric vibrations will have the smaller extinction coefficient.
ry
ra
IR spectrum
ib
2lR-bands
U
T8P structure
yl
Terminal
m
CO
he
2200 2100 2000 1900
+-----
_
v, cm
-1
lc
ea
Fig. 9.4.11.3a Infrared spectra of [Fe(COh] in the C-O stretching region (2 IR-bonds ~ TBP not SP).
th
e/
t.m
c
0
'e(/)n Forbidden
'E
(/)
transitions
c A1 (weakly
a3
active)
e
t=
er
1 81
i
H
2000 1900 2000 1900

1
+--- v, (cm- )
+--- v, 1
k
(cm- )
lic
cis-[Mo(CO)4{P(OPh)3}2] trans-[Mo(CO)4{P(OPh)3}2]
C2V [ 4 ir-bands (2A 1 + 8 1 + 8 2 ) 1 ir-band (E u)
D4h [ A 1g and 8 1g : IR-inactive but
C
Raman active.
Fig.9.4.11.3b Infrared spectra (in the C-O stretching region) of cis- and trans-isomers of [Mo(CO)4{P(OPh)3h].
Note: Ideally, in the trans-complex of D 4h symmetry, the A lg and Big modes are IR-inactive. But, asymmetry of the ligand
lowers the symmetry of the molecule as a whole to some extent and it makes the IR-forbidden A ig and Big modes weakly
active. The IR-active C-O stretching modes are shown in Fig. 9.4.11.1.
The basis of this rule is that in a symmetric vibration, dipole moment of the molecule changes less
compared to that caused by an asymmetric vibration. Intensity ofa particular band depends roughly on
the degree ofdipole moment change occurring during that particular mode of vibration (see Sec. 12.1).
Thus, the intensity of the asymmetric C-O stretching (e.g. B b B2) will be higher than that of
the symmetric C-O stretching (e.g. AI). It has been experimentally verified (Fig. 9.4.11.3b) for
cis-[Mo(CO)4] {P(OPh)3 }2].
Here it may be mentioned that for the intensity of IR-bands of the C-O stretching, the metal~CO
n-bonding effect has got some influence. The better 1t-bonding producing the weaker C-O bonds
leads to the higher intensity. Thus for the isoelectronic species, intensity follows the sequence,
ry
[V(CO)6]-' [Cr(CO)6]' [Mn(CO)6]+
ra
Decreasing trend of 1t-bonding
ib
Decreasing trend of intensity of the IR-band due to the C-O stretching
yl
(C) Effect of stereochemical nonrigidity on the number of IR-bands: In solid state,
[Fe2(CO)4(lls-CsHs)2] shows one IR band at 1781 cm- I (for the bridging CO group) and one IR band
m
at - 2000 cm- I for the terminal CO groups. The bridging two CO groups are almost colinear and this
is why, they show only one band. In solid state, the compound adopts the trans-structure
he
(C 2h symmetry) in which the terminal trans-CO groups give one band (-2000 em-I). In solution, the IR-
band due to the terminal CO group is split into a doublet (Figs. 9.4.11.3c, 9.4.11.4c). It is due to the
lc
stereochemical nonrigidity leading to the cis- and trans- isomers along with some nonbridged structure.
In fact, in solution, 4 interconverting isomers remain. These are: cis- and trans- bridged forms; trans-
ea
nonbridged form (nonpolar) and polar cis-nonbridged form.
th
o o
e/
~ !I co oe II
~ ,..--e~ / "" ,..--e~ /
CO
o
t.m
Bridged u
~Fe
@Fe)~Fb
forms Fe C>
c:
/"~ ~ '0
oe!le '0dI "'0
~
e
o o 1 i i i
(trans-form) v (cm- ) 200019001800
er
(cis-form)
[(lls-Cp)(OC)2Fe- Fe(CO)2(lls-Cp)]
H
(nonbrldged isomers, both polar and nonpolar forms)
Fig. 9.4.11.3c Isomeric forms of [FeiCO)/1l5-Cp)2] and the IR-active bands (for C-O stretching) when studied in
k
solution,
lic
(D) Position of Vco: V eo of free CO arises at 2143 cm- I but depending on the efficiency of metal ~
CO n bonding involving the n* -MO of CO, the position of veo is shifted towards the lower frequency
C
(cf. Sec. 9.4.6). In this discussion, the negligible effect of M f - CO a-bonding on v eo is ignored for the
sake of smplicity. In reality, this a-bonding slightly shifts the veo towards the higher frequency.
(E) Positions of vco for the terminal and bridging CO groups in neutral molecules: We have
already mentioned that the positions of v eo can identify the bridging and terminal CO groups (cf. Sec.
9.4.6).
Terminal-CO Jl2-CO Jl3- CO
Veo (em-I): -1850-2140 -1700-1850 -1600-1720
(F) Examples and illustrations for shifting of vco:
(a) Tetrahedral carbonyls (isoelectronic series):
[Fe(CO)4]2- [CO(CO)4]- [Ni(CO)4]

1788 2002, 1890 2131,2058
(i) decreasing trend of C-O bond length
(ii) increasing trend of C-O bond order
(iii) increasing trend of v co
(iv) Decreasing trend of negative charge and increasing trend
ry
(periodic trend) of electronegativity at the metal centre.
(v) Decreasing trend of M ~ 1t*-MO (CO) back bonding.
ra
In the above isoelectronic series, with the increase of net negative charge, the M ~ CO 1t-back
bonding increases and consequently, the ir-stretching frequency, i.e. veo shifts gradually towards the
ib
lower frequency. In fact, the higher negative charge favours the metal ~ CO n-back bonding more and
yl
it reduces the C-O bond order. This explains the shifting of Yeo.
Note: Here it must be mentioned that besides the effect of overall charge, the electronegativity in-
m
creases for the d-block elements along the series from left to rigttt (a periodic trend). Thus, the n-back
bonding is least favoured in [Ni(CO)4]. In fact, both the effect of net charge and electronegativity
he
sequence (Ni ) Co ) Fe) shollid be considered and both the factors operate here in the same direction.
Obviously, the effect of net charge is the more predominant factor.
(b) Octahedral carbonyls (isoelectronic series): lc
ea
Increasing trend of metal~ 1t* -MO(CO) back bonding
(
[Ti(CO)6]2- [V(CO)6]- [Cr(CO)6] [Mn(CO)6]+ [Fe(CO)6]2+

th
veo(cm- l ): -1745 -1860 -2000 -2090 -2205

e/
(i) decreasing trend of overall negative charge

(ii) increasing trend of electronegativity at the metal centre.
t.m
(iii) decreasing trend of M ~ CO n-back bonding.

(iv) increasing trend of C-O bond order and Yeo.
The shifting of v eo in the above isoelectronic species of carbonyls can be explained as in the case
e
of tetrahedral isoelectronic carbonyls.

[V(CO)6]- [Cr(CO)6]
er
-460 -441
H
(i) decreasing trend of M ~ CO 1t-back bonding

(ii) decreasing trend of M-C bond order.
k
(iii) decreasing trend of VM-C.

lic
The decreasing trend of M~CO n-back bonding can be explained in terms of the coupled effect of
net charge and electronegativity of the metal centre. This explains the sequence of v M - C .
C
(c) Magnitude of vco depending on the nature of other ligands:

[Cr(CO)6] [Cr(CO)3(dien)]
veo(cm- l ): -2000 -1900,-1760
[Mn(CO)6]+ [Mn(CO)3(dien)]+
veo (em-I): -2090 -2020,-1900
In [M(CO)6]' three t2g orbitals participate in n-back bonding with the 6 CO groups giving rise to
1
average "2 n-bond order in each M-C linkage. On the other hand, in [M(CO)3(dien)], the three t 2g
orbitals participate in n-back bonding with the three CO groups and consequently the average n-bond
order in M-C linkage is higher i.e. less bond order in the CO linkage. The a-donor property of three
sp3-N sites of dien also favours the M ~ CO n-back bonding. This aspect has been already discussed
in detail earlier (Sec. 9.4.10).
Position of v co for the CO group at the trans-position of the PPh 3 ligand in [Cr(CO)s(PPh3)] has
been also discussed in Sec. 9.4.10. .
(d) Position of vco for the carbonyls of same group:
ry
[Fe(CO)s] [Ru(CO)s] [Os(CO)s]
-2002, -1980 -2000, -2035 -2005, -2045
ra
vco == 2000 cm-1 for [M(CO)6] where M = Cr, Mo, W.
ib
It indicates that vco remains more or less the same for the metal carbonyls of the congeners. In fact,
many factors jointly determine the efficiency of the metal-carbonyl bonding and some of the factors
yl
oppose mutually. For example, the higher effective nuclear charge and higher electronegativity of
m
the heavier congeners favour the M f- CO a-donation (which slightly enhances the vco value, cf. Secs.
9.4.10,9.4.12) but disfavour the M ~ CO n-back bonding (which reduces the v co value). Larger size
he
of the heavier congeners reduces the steric crowding while the more stenc crowding for the lighter
congeners weakens the M-C bond (i.e. vco increases). The larger size of the d-orbitals of the heavier
lc
congeners disfavours the M ~ CO n-back bonding while it is relatively more favoured for the lighter
congeners. Probably, the combined effects of all these factors keep the vco value more or less the same
ea
for the congeners of a particular group (see Question No. 40).
(e) Identification of the bridging CO group:
th
[Fe2(CO)9] [C0 2( CO )8]; solid [C02(CO )8]; in solution

(Bridged Structure) (Nonbridged structure)
e/
2020, 2082 2000-2050* 1990-2060*

(terminal CO) (terminal CO) (terminal CO)
t.m
1830 1860, 1886

(Jl2-CO) (J.l2-CO) .
*A number of peaks.
e
• [Ni 2(CO)2(Tl s-Cp)2]: vco appears at 1897 cm- l and 1857 cm- l . It indicates that both the CO
er
groups remain as the bridging CO groups. The two Jl2-CO groups are not colinear.
H
k
lic
C
Heating
-2eO
) [(1l5- Cp)Mo(CO)2]2; (see Fig. 12.1.17.1)
V eo = 1915, 1960 cm- l
= 1859, 1890 cm- l V eo
(terminal CO group) (Nearly linear bridging CO group; not purely
terminal CO group)
• [Fe2(CO)9] and [Co2(CO)s]: The veo (terminal) ) v eo (Jl2-CO) is experimentally verified in
ry
[Fe2(CO)9] and solid [C0 2(CO)8] (Fig. 9.4.11.4a).
Existence of both the Jl2-CO group (Veo ~ 1830-1870 em-I) and terminal CO group (v eo :::: 2000-
ra
2080 em-I) in [Fe2(CO)9] and [C0 2(CO)8] has been experimentally verified by X-ray studies.
• [Mn2(CO)10]: In [Mn2(CO)IO], no signal in the range 1700-1860 cm- 1 is obtained. It indicates the
ib
absence of any bridging CO group.
• [F~(CO)12] and [OS3(CO)12]: The IR-spectra of [Fe 3(CO)12] are complicated to analyze because
yl
of its fluxional character and its interaction with lattice or Fermi resonance.
m
In [OS3(CO)12]' no signal below 2000 cm- 1 is noted and v eo appears only in the range) 2000 cm- 1
(Fig. 9.4.11.4b). It indicates that in OS3(CO)12 there is no bridging CO group.
he
• [C~4(CO)12] and [Ir4(CO)12]: Position ofv eo indicates the presence of both bridging and terminal
CO groups in [Co4 (CO)12] but only terminal CO group in [Ir4 (CO)12]. Interestingly, in the mixed metal
lc
compound, [Ir2Co2(CO) 12] both types of CO group are indicated from the position of Yeo.
• [Fe2(CO)4(Tls-Cp)2]: It shows v eo ~ 1800 cm-1(i.e. bridging CO) and ~ 2000 cm- 1(i.e. terminal
ea
CO group) (Figs. 9.4.11.3c; 4c). Two bands for the terminal CO groups and one band for the
bridging CO groups appear. One band for the bridging two CO groups indicates that these two
th
bridging CO groups are colinear (ef the nonlinear Jl2-CO groups in [Ni 2(CO)2(1l5-Cp)2]).
v eo ::::: 1830 cm- 1
e/
t.m
., 0 0
C C
e
1
/ "'" / " 2082 cm-
00 C CO
er
o
(a) [Fe2(CO)g]
H
k
i
lic
t All
C
terminal
c:: CO groups
o
"00
rn
"Ern
LJ c::
ctS
Terminal CO Bridging CO t=
2200 21 00 2000 1900 1800 1700
1
v (cm- )
2150 2100 2050 2000 1950 '1900
(a)
1
v (cm- )
(b)
• Splitting of the band for terminal CO

groups indicates the steriochemical
nonrigidity (cf. Fig. 9.4.11.3c).
o
IIC
ry
5 5
(11 -Cp) . / (YJ -Cp)
/~ Fe / ( O farm )
ra
" " Fe CIS-
/ "'" / ' ~ CO
ib
OC C
II
yl
o
m
• A single band for the two bridging
he
I I L....!....J CO groups indicates that the bridging
CO groups are colinear.
Terminal CO Bri~ging CO
• For the trans-isomer one band for the
2000 1900 1800 1700
lc terminal CO groups.
ea
1
+-- v (cm- )
(c)
th
Fig. 9.4.11.4 Infrared spectra (for the C-O stretching) of (a) [Fe/CO)9]' (b) [OS~(CO)12] and (c) cis-[Fe2(CO)/1l~
Cp)2]' Note: In the solid state, [Fe/CO)/1'f'-Cp)2] adopts the trans-fonn for which there is only one band for the
e/
tenninal CO groups. In the cis- form, this band splits into a doublet «(f Fig. 9.4.ll.3c).
(G) Limitation in identifying the nature of CO group from the position of vco: The favourable
t.m
factors to enhance the metal ~ CO Tt-back bonding may shift the veo for the terminal CO towards the
lower frequency significantly. The said 'It-bonding is enhanced for:
(i) presence of the good a-donor ligands and absence of other competing Tt-acid ligands;
e
(ii) presence of the good a-donor ligands with poor or no Tt-acceptor property (e.g. PPh 3 );
er
(iii) overall increased negative charge on the complex and reduced electror'~gativity of the nletal centre.
These favourable factors may increase the metal ~ CO Tt-back bonding to such an extent that vco
H
for the terminal CO groups rnay be shifted in the range normally found for the J.l2-CO groups. For
example, in [Mo(CO)3(dien)], CO stretching frequency arises at ~ 1760 cm- I ; in [Fe(COtd 2-, v co ap-
k
pears at ~ 1780 cm- I ; in [Ti(CO)6]2-, vco appears at -1750 CI11- 1; etc. These stretching frequencies
lic
normally lie in the range of J.l2-CO groups but in the said complexes there is no J.l2-CO group.
(H) Effect of other coordinated ligands on vco: It has been already illustrated (Sec. 9.4.10) for
C
[M(CO)6] vs. [M(COh(dien)] (M = Cr, Mo) where in the mixed ligand complex, dien has substituted
three CO groups. The ligand dien is non-pi-bonding itself and consequently per CO group, more Inetal
electron cloud is available for the metal ~ CO Tt-back bonding in [lVI(CO)3(dien)J compared to that in
[M(CO)6]' This is why, v eo drops in [M(dien)(CO)3] compared to that in [M(CO)oJ. Now let us consider
some other examples .
• [RMn(CO)s] (R = CH 3, CF3 ): CF 3-group is more electron withdrawing than CH 3. This is why,
in [(F 3C)Mn(CO):d, relatively less electron is available on the metal centre for the back donation
to CO. Consequently, veo becomes higher in [(F3C)Mn(CO)s] and it explains the sequence:
• vco (em-I): 2110, 20] 2, 1990 (for [(H 3C)Mn(CO)s]); 2134,2043,2019 (for [(F3 C)Mn(CO)s])
ry
/CO
OC--Mo
ra
I ~BF3
ib
CO
yl
In the BF3-adduct, veo appears at a higher frequency (cf the electron withdrawing inductive effect
of BF3 ) and number of absorption bands increases. Increase in the number of absorption band occurs
m
due to reduction of symmetry on BF 3 attack.
Note: Shifting of veo to the higher frequency and increase in the number of absorption bands cannot
he
be explained by considering the attack of BF3 on the coordinated CO.
(I) Effect of other 0'- and x-bonding ligand (L) on vco: Positions of veo in different compounds
lc
like [M(CO)5L], [M(CO)4L2] depend on the nature of L. The important observations are:
(i) If L is a good a-donor ligand, it will favour the metal ~ CO n-bonding (cf Sec. 9.4.10). But if
ea
L shows the electron l-vithdrawing inductive effect through the a-bond, it will disfavour the said
n-back bonding (cf the effect of halide; Sec. 9.4.18). This aspect has been illustrated in (H) of this
th
section.
(ii) If L is a x-donor ligand (e.g. Br-), then M-CO n-back bonding is strengthened and veo drops i.e.
e/
v eo shifts to lower frequency compared to that of [M(CO)6]. Here it must be mentioned that the
t.m
halides can also withdraw the electron cloud from the metal centre due to the electron withdraw-
ing inductive effect through the a-bond. It will disfavour the M~CO n-bonding.
(iii) If L is a better x-acceptor ligand (e.g. NO+, PF3 etc.) than CO, then metal to CO n-back bonding
will be weakened and veo shifts to the higher frequency.
e
er
x
H
k
~---+ y
lic
z
C
Fig. 9.4.11.5 Competitive n-bonding interaction in the mixed carbonyls (say [M(COhL]) (cf Fig. 10.2.1.1).
(iv) If L is a weaker x-acceptor ligand (e.g. PR 3 , PCl 3 etc.) than CO, then metal to CO n-back
bonding will be relatively strengthened and veo will shift to the lower frequency.
ORGANOMETALLICS AND METAL CARBONYLS: It-ACID METAL COMPLEXES 1339
(Note: By considering the shifting of veo with the variation of L in [M(CO)5L], the spectrochemi-
cal series of L can be constructed)
(v) For the 7t-acceptor ligand L, the change of v eo for the trans-CO group (with respect to L) is
twice as much as observed for the cis-CO group i. e. metal ---7 CO 1t-back bonding is affected more
for the trans-CO group.
ry
Effect of 7t-acceptor ligand (L) on the CO group at the cis- and trans-positions
ra
• The a-donor property (aL) i.e. inductive effect of L will almost equally affect the CO group
at the cis- and trans-positions.
ib
• The 7t-acceptance (7tL) property of L will affect the n-bonding property of the CO group
through two metal d-orbitals when the CO group is at the trans-position and through one metal
yl
d-orbital when the CO-group is at the cis-position.
Thus, the 1t-bonding property ofL affects the 1t-bonding property ofthe trans-CO group two
m
times more than that of the cis-CO group.
he
The effect of the n-bonding (i. e. 7t-acceptance) properties of L on the bonding properties of CO can
be understood by considering the competitive 7t-bonding effect (Fig. 9.4.11.5). The a-donor property
lc
(al) i.e. inductive effect of L will affect the bonding property of the CO group almost equally for both
ea
the cis- and trans- positions. However, n-bonding property of L enters into competition with that of the
CO groups in different magnitudes for the cis- and trans-positions.
From Fig. 9.4.11.5, it is evident that the trans-CO and L ligand mutually compete for two metal
th
dft-orbitals while the cis-CO and L ligand mutually compete for one metal dft-orbital.
• With reference to the Fig. 9.4.11.5, it is evident that if L and CO are at the trans- positions, they
e/
can compete for the dx.v and dy : orbitals of metal i.e.

t.m
n*(px)(CO)trans-dxy,(M)-dX).(L)
1t*(P J( CO )trans-dy:(M)-dy:(L)
• If L and CO are at the cis- positions, then they mutually compete for one metal d-orbital i.e.
e
n*(p.J(CO)cis-dxy,(M)-dxy(L)
er
The n*(pJ(CO)cis-dx/M) interaction is not in competition with L (when cis- to the competing CO
group) because the dxz. orbital of L is not in a suitable position to make any n-type interaction with the
H
metal dx: orbital.

By considering the competitive 7t-bonding effect between L and CO, it has been concluded (Ref.
k
W.A.G. Graham, Inorg. Chern. 7, 315, 1968):

lic
• change in force constant for CO (trans-L) = dal + 2dnl

• change in force constant for CO (cis-L) = dal + dn l
C
a l gives the measure a-basicity of L; n l gives the measure of n-acidity of L. Higher a l will favour
the metal ---7 CO n-back bonding to reduce the force constant of the CO stretching. Higher n L will
reduce, the metal ---7 CO n-back bonding to increase the force constant of CO stretching.
• If L (e.g. NO+) is a better 7t-acceptor ligand than CO, then metal to CO n-back bonding is more
restricted for the trans-CO group than for the cis-CO group. In such cases, VCO(trans) ) VCO(cis) ) vco (in
unsubstituted compound).
• If L is a weaker 7t-acid ligand than CO, then vco for the trans-CO will be less than that for the
cis-CO (with respect to L but trans with respect to CO). It will lead to: VCO(trans) ( VCO(cis) ( vco (in
unsubstituted compound). This is illustrated for [Mo(CO)s(PR3 )].
1340 FUNDAMENTAL CO'NCEPTS OF INORGANIC CHEMISTRY
Each cis-CO group is trans- to another CO i.e. cis-CO groups experience a stronger competition than
the trans-CO-group that experiences a weaker competition from PR 3.
co
~1~~-r7ro
(cis)
~P~---~-7fR3
~
Competitive IT-bonding:
ry
, ,
, ' ty10~:
I , ' ~O~:' CO (in [M(CO)6l > C0cis > COtrans
ra
i-------co
1 I 1 , I 1
, I 1
/
, I ,
/
(tr~)- - - - - - - - (cis) 06--------i------- co
ib
CO CO
yl
eo = xcm-
V 1
(cis)
m
Veo (trans) = Y ( Veo (cis) = Z ( Veo (in [M(CO)6]) '= x
(PR 3 is a weaker n-acid ligand than CO)
he
~"ig. 9.4.11.6 Relative positions of veo for the different CO groups in [Mo(CO)5(PR3 )] .
• !ac-[Mo(CO)3(PX 3)3]: The fac-isomer gives two ve - o ir-bands. The veo value follows the se-
lc
quence: PF 3 ) PCl 3 ) PCIPh 2 ) PMe3' Here PF 3 is the weakest a-donor and the strongest n-acceptor while
ea
PMe3 is the strongest a-donor and the weakest n-acceptor. Thus, Mo ~ CO n bonding is most favoured
for PX 3 = PMe3 while it is least favoured for PX 3 = PF 3 . It explains the order of Yeo.
Complex: jac-[Mo(COh(PF 3hl jac-[Mo(COh(PCI 3hl .!ac-[Mo(COh(PCIPh 2 hl jac[Mo(COh(PMe3hl
th
Veo (em-I): 2090, 2055 2040, 1990 1977. 1885 1945, 1854
(vi) L, a n-donor ligand favouring the metal to CO n-bonding more at the trans-position: For
e/
[Mn(CO)sX], (X = n-donor ligand like CI, Br:I), veo increases in the order: cis-CO) trans-CO;
t.m
CI ) Br ) I (Lf. Fig. 10.2.1.1).

(J) Determination of spectrochemical series for the n-bonding ligands from the shift of vco: In
[M(CO)sL], if L is a better n-acid ligand than CO, then in the competitive n-bonding, the Inetal ~ CO
n-bonding will be more weakened compared to that in the unsubstituted compound i.e. [M(CO)6]' If L
e
is a weaker n-acid ligand or a n-donor ligand, then i,n th~ substituted compound, the metal ~ CO
er
n-bonding will be more favoured. Thus we conclude:

• veo [for M(CO)6] ) veo [for M(CO)sL], L is a a-donor ligand or L is a weaker n-acceptor ligand
H
than CO i.e. L is a weaker field ligand than CO.

• veo for [M(CO)(J ( veo for [M(CO)5L], L is a stronger n-acid ligand than CO i.e. L is a stronger
k
field ligand than CO.

lic
Based on this idea, spectrochelnical series has been constituted as follows:

· dfild h NO+)PF3 )CO)AsCI,)PCI,)P(OR)3)PR 3
I.Jlgan Ie strengt : ( . . - .,
C
1t-acceptance
Note: Force constant for CO stretching runs as: jac-[Mo(CO)s(PF 3)] ) [Mo(CO)6]-Explain
(K) Effect of the a-donor ligand (L) in!ac-[M(CO)3L3]: The a-donor ligands (e.g. NH 3) enhances the
electron density on the metal centre to favour the metal ~ CO 1t-back donation. Absence of competitive
1t-bonding from the trans-direction in.fac-[M(CO)3L:d (L = a-donor ligand) also favours the M ~ CO
n-bonding (Lf. Fig. 9.4.11.5). It is illustrated below:
v eo (em-I): 2143 (free CO) ) [MO(CO)6] (2000) ) [Mo(COh(PPh 3)3] (1950) ) [Mo(CO):lNH 3 ):d
(1855) «(f increasing trend of Mo ~ CO n-bonding and a-donation to Mo: [MO(CO)3(NH 3 h] )
[Mo(CO).,(PPh 3)3] ) [MO(CO)6])'
The observation, V co [M(CO)3(dien)]<v co [M(CO)6] for M = Cr, Mo can be explained by

considering this argument (cf Sec. 9.4.10).
(L) [Ir(CO)(CI)(PPh3)2(X)(Y)]: For the a- and n-donor ligands (e.g. halides), veo increases with the
increase of electronegativity of X and Y. For the better n-acceptor ligands i.e. X, Y = PF 3 , NO+, etc.;
C 2F4, C 2(CN)4 replacing X, Y, veo increases veo(cm- 1) = 2067 (X =Y = I), 2075 (X =Y = CI). These
are discussed in Sec. 10.6.1.
ry
ra
CO substitution by other ligands in [M{CO)6l (ct. Sec. 10.2)
If CO is substituted by a weaker n-acid ligand like PR3, then gradually the M-CO bond becomes
ib
stronger because of the better metal ~ CO n-bonding. Thus subsequent substitutions becomes
yl
more difficult.
m
[MO(CO)6] excess PPh 3 ) [Mo(CO)3(PPh 3)3], (further substitution is not possible)
But if, the CO group is substituted by a better n-acid ligand like PF3 , then the M-CO bond
he
becomes gradually weakened because of the disfavour in the M ~ CO n-back bonding. In such
cases, all the CO groups may be substituted.
[M(CO)6]
excess PF3
lc
) [M(CO)6 _ n(PF3 )n], n = 1 - 6 for M = Cr, Mo
ea
[Ni(CO)4]
excess PF3
) [Ni(CO)4 _ x(PF3 )n], n =1- 4.
th
9.4.12 Unusual C-O Stretching Frequency and Nonclassical Carbonyls

e/
From the knowledge of the factors to determine the ease of metal ~ CO back bonding, we conclude
that the process is disfavoured under the following conditions:
t.m
cationic charge of the metal centre; high electronegativity or effective nuclear charge (Z*) of the
metal centre. (noted for the heavier congeners of specially Gr. 11, 12) and mismatch in energy
between the metal d-orbital and n*-MO of co.
e
Obviously, such carbonyls are less stable and the marginal stability arises from the only M f - CO
er
a-bonding. In such cases, because of the weakly anti bonding character of the HOMO of the CO group,
the said a-bonding slightly enhances the C-O bond order. Consequently, vco becomes slightly higher
H
than that of free CO. Such carbonyls are described as the nonclassical carbonyls. Example of such
carbonyls are:
k
[Pd(CO)4]2+, [Pt(CO)4]2+, [Ag(CO)]+, [Ag(CO)2]2+, [Au(CO)]+, [Hg(CO)2]2+, [OS(CO)6]2+, [lr(CO)6]3+,

lic
etc. Such cationic carbonyls have been isolated by using the large counter anions like [Sb2F 1d-,
[B(OTeFs)4]-' etc. The classical example is: [Ag(CO)][B(OTeFs)4] having veo :::: 2205 cm- I () veo =
C
2143 cm- 1 of free CO).
9.4.13 Effect of Pi-back Bonding and Magnitude of 10Dq in the Isoelectronic and
Isostructural Carbonyls
With the increase of the efficiency of metal ~ CO n-back bonding, the 10 Dq value should in~rease.
This n:-back bonding introduces the more positive charge on the metal centre and it should lead to a
higher crystal field splitting. In terms of MOT, in an octahedral complex, the 10 Dq value gives the
measure of energy difference between t28 and eg*. The n-back bonding involving the t28 orbital leads to
the stabilization of the t28 level. It causes the higher 10 Dq value. Thus it is reasonable to expect the
higher 10 Dq value for the better 7t-back bonding. But this expectation is not experimentally verified
for the following octahedral isoelectronic carbonyls.
[V(CO)6]- [Cr(CO)6] [Mn(CO)6]+
- v eo (cm- I ): 1860 2000 2090
I
- VM-C (cm- ): 460 441 416
ry
decreasing trend of M ~ CO 1t-back bonding
ra
25,500 32,200 41,050
ib
increasing trend
yl
To explain the observation, it is required to consider the effect of both overall charge and extent of
1t-back bonding on 10 Dq. With the increase of overall negative charge, the extent of 1t-back bonding
m
increases to increase the 10 Dq value. But with the increase of overall negative charge, the 10 Dq value
decreases. Thus, effects of these two factors mutually oppose. In fact, the direct effect of overall
he
charge on 10 Dq is relatively more important. It explains the observed sequence of 10 Dq value.
lc
9.4.14 Structural and Bonding Properties in the Polynuclear Carbonyls
(cf. Sec. 9.4.2 of this chapter and Sec. 12.8.5. of Vol. 3)
ea
(A) Characteristics of polynuclear carbonyls: Some important aspects of carbonyl clusters i.e.
polynuclear carbonyls are summarized here.
th
• LNCC and HNCC (Fig. 9.4.2.1): Polynuclear carbonyls i.e. carbonyl clusters containing up to
four m~tal atoms are described as the low nuclearity carbonyl clusters (LNCC) while those
e/
having five or more metal atoms are described as the high nuclearity carbonyl clusters (HNCC).
t.m
LNCCs generally follow the 18e-rule but the higher members of HNCC sometimes disobey the
18e-rule.
• Mixed metal clusters: The polynuclear carbonyls involving only one type of metal atoms are
described as the homonuclear carbonyls, e.g. [Fe3(CO)I2], [Ir4(CO)I2], etc. When different met-
e
als are involved, they are described as heteronuclear carbonyls, e.g. [ReMn(CO)lO]' [Ir2C02(CO)12],
er
[MnCo(CO)9]' [Ru2Fe(CO)I2], etc. (cf. Fig. 9.4.2.1).

• Mixed ligand clusters: Sometimes, other ligands like NO, Cp, etc. are also involved, e.g.
H
[Fe2(CO)4(llS-Cp)2] i.e. [(llS-Cp)2Fe2(CO)2(J.l2-CO)2], [M0 2(CO)6(llS-Cp )2],

[Ni2(J.l2-CO)2(lls-Cp)2] etc. (cf. Fig. 9.4.2.1).
k
• Cluster extension by hetero-atoms like C, N, S, etc.: Sometimes, the clusters may be extended
lic
by the hetero-atoms like, C, N, S, etc. e.g. [Fes(J.ls-C)(CO)IS]' [Fe4(J.l4-C)(CO)I2]2-, [C03(CH)(CO)9],

[Fe3(CO)9S2], [RU6(J.l6-C)(CO)17] etc. (cf. Fig. 9.4.2.1).
C
• Polynuclear carbonyl halides: These are produced through the halide bridges (cf. Sec. 9.4.18).
• Metal-metal bonds preferred for the heavier congeners: Polynuclear carbonyls contain the
M-M bonds. This metal-metal bonding is favoured for the low oxidation states because positive
oxidation state disfavours the process in two ways.
(i) Electrostatic repulsion between the positively charged metal centres.
(ii) High positive charge contracts the d-orbitals which actually undergo overlapping to form the
metal-metal bond. The contraction of d-orbital in size disfavours the overlapping process.
The metal-metal bonding is generally favoured for the heavier congeners characterized by large
cohesive energies in the metallic crystals. This is favoured because of the following reasons:
(i) Size of the d-orbitals is relatively larger (cf relativistic expansion of d-orbitals, Vol. 1) for
the heavier congeners and this favours the overlapping between the d-orbitals of the heavier
congeners.
(ii) Large cohesive energies in the metallic crystals among the refractory metals like Os, Ir, etc.
favour the metal-metal bond formation. In fact, the energy released in the M-CO bondformation
cannot break down all the existing moetal-metal bonds.
ry
It is illustrated for the Fe-group metals. For Fe and Ru, the clusters may contain upto maximum
ra
4-5 metal centres but, for Os, higher carbonyls like [OS6(CO)lS], [OS7(CO)21], [OSS(CO)23], [OS17(CO)36]2-
etc. are known.
ib
• Colour: Generally, the mononuclear carbonyls are colourless while the polynuclear charbonyls
are coloured (see Sec. 9.4.16 for explanation).
yl
• Two types of CO groups and carbonyls of the heavier congeners favouring the nonbridged
m
structure: In the mononuclear carbonyls, only one type of CO groups (called the terminal CO groups
which form the linear M-C-O segments) exists. But in the polynuclear carbonyls, depending on the
he
conditions, two types of CO-groups may exist.
(i) Terminal CO group, i.e. TIl_CO.
lc
(ii) Bridging CO-group - which are mainly of two types, i.e. J.!2-CO and J.!3-CO (known as also
apical CO group). J.!2-CO commonly occurs while J.!3-CO occurs only in some limited cases.
ea
The bridging CO groups generally span along the M-M bonds. Thus in the polynuclear carbonyls,
there may be two types of M-M bonds.
th
(i) M-M bonds alone;

(ii) M-M bonds containing the bridging CO group.
e/
It has been already mentioned (Sec. 9.4.4) that the bridging CO groups (generally J.!2-CO) prevail
in the carbonyls of lighter congeners. On the other hand, the heavier congeners prefer the nonbridged
t.m
structure. In some cases (e.g. [C0 2(CO)s)], there may be a structural equilibrium mixture due to the
bridged-nonbridged tautomerism.
For the polycarbonyls of heavier congeners, the relatively longer metal-metal bond distance disfavours
e
the positioning of CO as a bridging one to spa~ over the M-M bond. To place a bridging CO group
er
along the longer M-M bond, either the M- C -M bond angle opens up, or ~he M-C distance
elongates or both. These requirements will destabilize system. Generally, the M-C -M angle lies in
H
.the range of 90°, but for the larger M-M distance, the bond angle becomes large to destabilize the
bridged systems. Actually, in such large bond angles, electron delocalization involving the metal
k
d-orbitals and the orbitals of CO is disfavoured but electron delocalization is essentially required for the
lic
stability of the carbonyls. This is why, for the larger metal-metal distance produced by the heavier.
congeners, the terminal CO groups are preferred over the bridging CO groups. This aspect has
C
been illustrated in Sec. 9.4.4.
(L = CO, C.N. = 7) (L = CO; C.N. = 6)

(Sterically disfavoured; nonexistent) (Sterically tolerable; existent)
o
o
CO I CO
0
oc'" I / C " ' " I/CO I

C C
I
Mn Mn
OC'" ~ /CO
oc / CO
I"'" ~ / COCO
I"'-
ry
OC-Co Co-CO
OC
/ "'- CO
ra
o
(Sterically disfavoured, C.N. = 7; nonexistent) (Sterically tolerable, C.N. 6; existent)
ib
(Relatively longer Mn-Mn distance also disfavouring (Relatively shorter Co-Co distance favouring
the bridging CO groups) the bridging CO groups)
yl
Fig.9.4.14.1 Possible dimeric structures of some carbonyls maintaining the 18e-rule.
m
• Steric factor and metal-metal distance to determine the nature of CO group: The above
discussion indicates that the bridging CO groups are relatively preferred in the carbonyls of
he
lighter congeners while the nonbridged structures are preferred in the carbonyls of heavier
congeners. But the conclusion is not so straight-forward. [Mn2(CO)1O] can be argued to have a
lc
bridged structure e.g. [Mn2(CO)S(J.l2-CO)2] by comparing the structure of the bridged tautomer of
[C0 2(CO)s] i.e. [~02(CO)6(J.l2-CO)2]. But, for [Mn2(CO)1O], the bridged structure does not exist.
ea
The given explanation is that according to the periodic trend of atomic radii, the Co-Co bond is
shorter than the Mn-Mn bond. This is why, bridging along the Co-Co bond is possible but it is
th
not possible for the Mn-Mn linkage. But it may be argued that besides the M-M distance factor,
the steric factor is also contributing for the nonexistence of the bridged structure of [Mn2(CO)1O].
e/
In the bridged structure, i.e. [Mn2(CO)8(J.l2-CO)2], the coordination number of Mn becomes 7

t.m
(which depends on the number of bridging CO groups) while in the corresponding bridged structure
of [C0 2(CO)s], the coordination number is 6 which is quite likely. But the coordination number
7 for Mn is quite unlikely because of the steric grounds. In fact, [V(CO)6] (17e configuration)
denies to undergo dimerisation to attain 18e configuration because it will lead to 7 coordination
e
number which is sterically crowded. In fact, [V(CO)6] is easily reduced to [V(CO)6]- to attain
er
the 18e configuration maintaining the 6 coordination number.

H
Examples of some polynuclear carbonyls indicating the nature of modes

of binding of CO (cf. Fig. 9.4.2.1)
k
[Fe2(CO)9] i.e. [Fe2(CO)6(J.l2-CO)3]; [Fe3(CO)12] i.e. [Fe3(CO)lO(J.l2-CO)2]; [M 3(CO)12]

(M =Ru, Os, with no bridging CO); [M 4(CO)12] i.e. [M4(CO)9(J.l2-CO)3] (M =Co, Rh); [Ir4(CO)12]
lic
(no J.l2-CO); [OS4(CO)lS] (no bridging CO); [Rh 6(CO)16] i.e. [Rh6(CO)12(J.l3-CO)4],
[M(CO)(J.l2-CO) (l1S-Cp)]2 (M = Fe, Ru); [Ni(J.l2-CO)(l1s-Cp)]2
C
-Exceptional cases where CO binds with the 4 metal centres as in [HFe4(CO)lS]- where one
CO group binds with three Fe-centres as a J.l3-CO groups and it binds simultaneously with the
fourth metal centre by using the n-electron cloud of the carbon-oxygen bond (see Sec. 9.4.6).
Thus here the CO group acts as a 4e donor (20 + 2n) ligand.
(B) VBT model for some representative binuclear carbonyls:

• VBT model of binuclear carbonyls, i.e. [M 2(CO)lO], M = Mn, Tc, Re: The corresponding monomeric
species, [M(CO)s] are radicals bearing an unpaired electron each with the 17e-configuration. By J
dimerization, having the M-M bond, they can attain the 18e configuration where 6 coordination number
is attained. Thus, in the dimer, the steric crowding is tolerable (cf. dimerization of 17e [V(CO)6] is
disfavoured because the C.N. 7 in the dimer is not tolerable).
In [M(CO)5]' the metal centre is cPSp3 hybridized having an unpaired electron in one cPSp3 hybrid
orbital. The cPSp3 hybrid orbitals bearing the unpaired electrons undergo overlapping giving rise to
[M 2(CO)1O] in which each metal centre is octahedrally surrounded where 5 coordination sites are
ry
occupied by the CO groups while the sixth position is occupied by the other metal. The OC-M-M-CO
segment is linear with two square planar segements having the CO groups in a staggered condition
ra
to minimize the steric repulsion (cf. Fig. 9.4.14.2). The bonding scheme is shown in Fig. 9.4.14.2.
ib
(n -1)d ns np
~ ~
yl
[M(CO)5]:
A
t t t t t
m
CO CO CO CO CO
he
M - M cr bond
V
[M(CO)5]: EJlc ~
t t t t t
ea
M = Mn, Tc, Re CO CO CO CO CO
..J
~
th
2
d sp 3 hybrid orbitals
(a)
e/
t.m
m
C
~-.------~
~",' n ~,
---,
e
0
C
0
C
/------
,
er
DC CO
Staggered orientations
H
274 pm _--- _ / of the square planar

segments
DC O==y~ ~
k
Mn~,_
C
0
C
0 :/t_----c==o
I
lic
/ ----m
o
C
(b) (Nonexistent) (c)
Fig. 9.4.14.2 Structure and bondinJ of [Mn2(CO)IO] (a) Hybridisation scheme for the nonbridged structure; (b) Hypo-
thetical bridged strucutre; (c) Nonbridged structure.
• VBT model of [Co2(CO)g]: Experimental evidence indicates that in solution there is an equilibrium
between the bridged and nonbridged tautomers, i. e.
[(OC)4CO-CO(CO)4] H [C02(CO)6(~2-CO)2]
In fact, energy difference between the two forms is not very high and the kinetic barrier for their
mutual inter-conversion is not too high. At a low temperature, the bridged structure predominates while
the nonbridged structure tends to appear at a relatively higher temperature. At a much higher temperature,
the third unknown structure may prevail.
r-------~------
3d 4s 4p
ry
Co:
One centre in
[]] ~
':' ':' A
t t t
ra
[Co 2 (CO)s]
J12-~O J12- CO CO CO CO
ib
: Co-Co
: (bent a bond)
v v V
yl
Co:
Other centre in rn~
m
[Co 2 (CO)s] t t t
CO CO CO
he
lc
----_.-/"--._----
dSp3
ea
')
3d 4s 4p
~ ~
Co:
th
One centre in
[Co 2 (CO)s] A
: t t t t
e/
CO CO CO CO
Co-Co (a-bond)
t.m
V
Co:
Other centre in EJ~
[Co2 (CO)s] t t t t
e
CO CO CO CO
er
(b) [Co 2(CO)al (nonbridged structure)

H
~----? ,l\
k
~-0T--COI--.l':"'"_ _-:-,_' Co~\

lic
•• •
\J/ !I-~
C
\ I
\ I
(d) Nonbridged structure
• ~ L i.e., CO
(c) Bridged structure
Fig. 9.4.14.3 Bonding and structure of [C0 2(CO)8]' (a) Hybridisation scheme for the bridged structure; (b) Hybridisation
scheme for the nonbridged structure; (c) Structure of the bridged structure; (d) Structure of the nonbridged structure.
ORGANOMETALLICS AND METAL CARBONYLS: n-ACID METAL COMPLEXES 134"'
In the bridged structure, [C0 2(CO)8], each Co-centre is tPsp3 hybridized to attain the octahedral
coordination. Each metal centre is having three singly filled hybrid orbitals, out of which one is
involved in the Co-Co bonding (a bent bond) while the other two orbitals participate in bonding with
the two bridging CO groups. This is shown in Fig. 9.4.14.3a.
Similarly, the bonding scheme in the nonbridged structure can be explained. Here, each Co-centre
is dSp3 hybridized to adopt the trigonal bipyramidal geometry. One hybrid orbital bearing an unpaired
ry
electron is utilized in making the Co-Co bond while the other 4 vacant hybrid orbitals are utilized for
accommodating the CO groups.
ra
• VBT model for [MnCo(CO)9] i.e. [(OC)sMn-Co(CO)4]: Structure of this heteronuclear carbonyl
can be explained by considering the tPSp3 hybridisation of Mn and dSp3 hybridisation of Co. The
ib
Mn-Co bond is formed by the overlapping of the tPsp3 hybrid orbital of Mn and dSp3 hybrid orbital
yl
of Co, each orbital bearing an unpaired electron.
• VBT model of [Fe2(CO)9]: Its structure is: [Fe2(CO)6(1l2-CO)3] i.e. three bridging J.l2-CO groups
m
and three terminal CO groups around each Fe-centre. Each Fe-centre is believed to be tPSp3 hybridized
in which three vacant hybrid orbitals are used to accommodate the terminal CO groups. The three
he
hybrid orbitals bearing the unpaired electrons are involved in bonding with the three bridging J.l2-CO
groups. To explain the diamagnetic character of the species, it is suggested that the unhybrid orbital
lc
bearing an unpaired electron on each Fe-centre participates in. a-bonding. In fact, the Fe-Fe distance
(246 pm) is almost the same as in met~llic iron. The bonding scheme is shown in Fig. 9.4.14.4.
ea
d2sp3
------~------
th
( 3d 4s 4p J'
[E] ~
e/
Fe:
AAA ~ ttt
t.m
CO CO CO
(o-bond) Fe-~eIl2~O Il~-eo 1l2+CO
• I
v v v
EEEJ
e
Fe:
er
t t t
CO CO CO
H
(a)
J12-L
k
lic
e :> L i.e., CO
C
(c)
(b)
Fig. 9.4.14.4 Structure and bonding of [FelCO)9]' (a) Hybridisation scheme; (b) and (c) structure of [Fe2(CO)9]'
(C) Molecular orbital theory of polynuclear carbonyls: This is very much complicated. However,
the bonding properties of the terminal and bridging CO groups can be interpreted in terms of M f- CO
a-donation and M ~ CO rc-donation working in a synergistic fashion. This aspect has been already
discussed (see Fig. 9.4.9.3).
9.4.15 Bonding and Structures of Polynuclear Carbonyls In Terms of Polyhedral
ry
Skeletal Electron PairTheory (PSPT)
This aspect has been discussed in detail in Sec. 12.8.5 of Vol. 3 of this book.
ra
9.4.16 Physical and Chemical Properties of Carbonyls in General
ib
A. Physical properties (ct. !able 9.4.2.2)
yl
(i) Physical state (ef Table 9.4.2.2): The typical mononuclear carbonyls [Ni(CO)4], [Fe(CO)5],
m
[Ru(CO)5] and [OS(CO)5] are the volatile liquids at an ordinary temperature while most other
carbonyls are volatile solids. These solids melt or decompose at low temperature.
he
(ii) Solubility: All are typically nonpolar covalent compounds and these are generally soluble in the
organic solvents. However, [Fe2(CO)9] is an exception and itis insoluble even in nonpolar solvents.
In water, carbonyIs very often decompose.
lc
(iii) Thermal stability: The mononuclear carbonyls are very much thelmally unstable (ef bond energy;
ea
- 150 kJ mol-I only). In fact, because of this low bond energy, they undergo decomposition very
easily upon heating or irradiation with the ultraviolet radiation to release the toxic CO. This is
why, the carbonyls, in general, are toxic and these should be handled carefully to avoid poisoning
th
by CO. [Ni(CO)4] is more toxic than CO because the inhaled [Ni(CO)4] decomposes in lungs to
e/
cause the nickel-plating in lungs.

(iv) Air-stability: The carbonyls are thermodynamically unstable with respect to aerial oxidation. But
t.m
some carbonyls, e.g. [M(CO)6] (M = Cr, Mo, W) are quite stable in air at an ordinary temperature
due to the kinetic reasons.
(v) Magnetic property: Most of the carbonyls are diamagnetic. However, [V(CO)6] is paramagnetic.
(vi) Colour: The mononuclear carbonyls are generally colourless but the polynuclear carbonyls are
e
often coloured and the intensity of colour increases with the increase of the number of metal
er
atoms. Colours of the polynuclear carbonyls arise from the electronic transitions among the
orbitals largely localised on the metal framework (ef. PSPT theory; Vol. 3).
H
B. Chemical properties
k
(i) Substitution reaction (see Sec. 10.2.6 for subsitution vs. cluster fragmentation reaction): Some
lic
or all CO groups may be substituted by the ligands like PX] (X = halogen), PR 3 , py, SR 2, OR 2,
RNC (isocyanide), diars, phen, unsaturated organic hydrocarbons like C 6H o, cycloheptatriene, etc.
C
[Ni(CO)4]~~~~L )[NiL 4 ](L =PF3 ,RNC); (mixed products may be also obtained).
[Fe(CO)5]+PPh J -co >[Fe(CO)4(PPh J )] :~'6 {Fe(CO)J(PPh J )2} (all CO groups

cannot be replaced; see Sec. 10.2).
[Cr(CO)6] -~o )[Cr(CO)r (L),,] (x + y = 6, L = monodentate ligand like PF 3 )·
If all the CO groups are replaced, then the product is described as homoleptic product, e.g.
[Ni(PF 3)4]' It happens so when the incoming ligand is a better or at least comparable as a
n-acceptor ligand with respect to CO (see Sec. 10.2).
The substitution occurs through the dissoci~t~ve path because the associative path will lead to a
transition state/intermediate of 20e-configuration which is energetically unfavourable (cf. 18e
rule). This aspect has been discussed in detail in Chapter 10. Substitution by the bulky ligands is
relatively unfavourable because of the steri~· factors. The steric hindrance can be measured in
terms of Tolman's cone angle (cf. Sec. 9.10). Apparently, it indicates the associative activation
but the rate retardation arises due to the steric hindrance in the product, i.e. the product formation
ry
is theromodynamically hindered. This aspect has been discussed in Chapter 10.
Cone angle: PPh 3(145°) ) PMe3(118°) ) CO(-95°).
ra
In fact, [MO(CO)6] reacts faster with PMe3 than with PPh 3.
ib
(ii) Disproportionation induced by the strong bases: This is illustrated in the following examples.
[;e(~O)J+3NaOH HF~(Co)J + Na2~03 + H20
yl
2
H 0) Na[
m
0 2+ l [ -2/3 J2- +4
Fe(CO)sJ+40H-~ Fe 3(CO)11 +CO~-+3CO+2H20
he
3[
The mechanistic aspects of this reaction has been discussed in Chapter 10.
Na[HFe(CO)4] is the starting material for many other important reactions. lc
ea
Hg2+
~ [H 2Fe(CO)4l -----3:.:~ [FeHg(CO)J
th
Na[HFe(CO)J -----3..
-2H+
metal-metal
Mn02 (aq.)
e/
Ph 3 PAuCI bond formation

j (-MnO) I--------~:.:~
-2HCI
[(Ph 3 PAu)2Fe(CO)J
}
t.m
OH- 2- H+
[Fe 3 (CO)12] .. [Fe 3 (CO)11l :.: [HFe 3 (CO)11l-
-HC0 3-
e
er
H
~02(~O)8J+12PY~2[~o(py)J2+[C~(CO)J: +8CO
k
3[
lic
(See Sec. 9.4.7E for more examples).

C
(iii) Reduction to metal carbonylate anions: '[he reducing agents commonly used are: Na in liquid
NH 3; Na-Hg in THF; KH in THF; Hg; H 2 ; etc.
[Fe(CO)s]+2Na Liq.NH 3 )Na 2 [Fe(CO)4]+CO;
[Cr(C0 6 )] Na-Hg,THF )Na 2 [Cr(CO)s]+CO
[Mn 2(CO)IO] +2KH THF) 2K[ Mn(CO)s] + H 2 ; Hg + [C02(CO)g]~Hg[ CO(CO)4]2
[Mn 2(CO)IO]+ H 2 ~2[ HMn(CO)s]; [C0 2(CO)g]+ H 2 ~2[ HCO(CO)4]

(iv) Oxidation to metal carbonyl halides:
[~nl(CO)IOJ+ Xl ~2[;;nx(co)J, X = CI, Br.

[~e(CO)5J+ Brl ~[F~Brl(CO)4 ] +CO
ry
(v) Reaction with NO: Many metal carbonyls may react with nitric oxide (NO) to form the metal
ra
carbonyl nitrosyls.
[Fe(CO)5] + 2NO ~ [Fe(CO)2(NO)2] + 3CO
ib
[C0 2(CO)g] + 2NO ~ 2[CO(CO)3(NO)] + 2CO
yl
(vi) Action of heat: Decomposition and polymerisation may occur.
m
180°C
[Ni(CO)4] )Ni+4CO
he
200°C
[Fe(CO)s] )Fe+5CO
3[Fe 2(CO)9 ]
sO°C
) 2[Fe 3 (CO)I2 ] + 3CO
lc
ea
1140 0
C
th
6Fe + 24CO \ \
e/
(vii) Reaction of the coordinated CO (cJ. Sec. 10.2.4, 10.3, 10.12): When electron delocalisation (i.e.
t.m
n-back bonding) is not very much strong (as in the case of carbonyls of heavier congeners or
early members having very few d-electrons), the nucleophilic attack can occur on C of the
coordinated CO group.
e
er
~ ~ ~ ~
M +:C~O: ~ M-C_O
H
Nu- = H-, R-, OH-, etc.

k
It is illustrated below.
lic
[(OC)5 M- C==O] + Li-R - - . Li+[(OC)5M-Cll-R]-

C
M = Mo, W
~ ElaO+ SF,
M<=f-RHCO)5] + Et2 0 + LiBF4

[
OEt
-
The last step of the reaction probably goes on as follows.
..
(OC)0C
5 ~
/l R
~ E( I"'Et
CO'
ry
ra
Et
The above reaction illustrates the synthesis of Fisher Carbene (cf. Sec. 10.3).
ib
o
yl
II] +
[Mn(CO)5(PPh 3)]++ RNH 2 ~
[ (Ph3P)(OC)4Mn-C-NH2R
m
-RNH; 1 (+excess ~NH2)
he
[(Ph3P)(OC)4Mn-~-NHR
lc ]
ea
Attack of OH- as a nucleophile on the coordinated CO group with the subsequent loss of CO 2 (as
HC0 3-) is supposed to be the crucial step ~in metal carbonyl catalysed water gas shift reaction
(WGS R, CO+H20~H2 +C0 2).
th
[LsM-COJ+ -OH~[LsM-~-OHJ ~-elimination )L sM-H+C0 2

e/
t.m
The mechanistic steps have been shown in detail in the reaction of [Fe(CO)5] with NaOH (cf
Sec.9.4.7E and Chapter 10).
e
Important Uses of Metal Carbonyls

er
(i) Extraction and purification of Ni by Mood's process through the formation of [Ni(CO)4]. (ii)
Iron-carbonyl as an antiknock agent in motor fuel (conventional but hazardous antiknock com-
H
pound, PbEt4 may be replaced by iron carbonyls). (iii) Preparation of finely divided iron oxide
particles (for industrial uses like polishing powder, colouring agent, etc.) through the thermal
k
decomposition of iron carbonyl. (iv) Instability of [Fe(CO)5] in light may be used to prepare the
lic
blueprints of drawings. (v) Iron carbonyl particles (uniform in size, shape and structure) may be
used in making the magnetic core of electronic equipments. (vi) Some metal carbonyls may be
C
used as catalysts in industrial activities, e.g. hydrogenation catalyst. (vii) Metal carbonyls in
organic synthesis (cf Collman's reagent and Na[Co(CO)4]).
9.4.17 Carbonylate Anions and Carbonyl Hydrides: Synthesis, Structure and

Properties (cf. Sees. 9.4.7E, 10.1, 10.4)
Synthesis: The reactions leading to synthesis of the carbonylate anions and carbonyl hydrides have
been discussed in Sec. 9.4.7E.
Structure: Fairly strong protonic character of some carbonyl hydrides [e.g. HCO(CO)4] raises a question
whether the H-atoms are directly bound to the metal centre or to the electronegative O-site. Electron
diffraction studies indicate that the M(CO)4 group is approximately tetrahedral in [H 2Fe(CO)4] and
[HCO(CO)4]. However, it has been now established that the H-atoms directly bind with the metal centre,
i.e. [H 2Fe(CO)4] is octahedral with the H-atoms in cis-positions (ef [Fe(CO)4]2-(Td), [HFe(CO)4]-
(TBP)); [HMn(CO)s] is octahedral, etc. If 'H' is treated as the H-ligand, the carbonyl hydrides should
be shown as, [Fe(CO)4(H)2], [Mn(CO)~H], etc. but conventionally these are written as [H 2Fe(CO)4],
[HMn(CO)s], etc. When the carbonyl lJydrides are strongly acidic, e.g. [HCO(CO)4] then it may be
ry
argued to represent as H[CO(CO)4] nOf as the hydrido complex. However, in such cases, the strong
acidity arises from the enhanced stability of the conjugate base, i.e. carbonylate anion. In some
ra
polynuclear carbonyls, 3c-2e M-H-M bridges may prevail (cf Fig. 9.4.2.1).
ib
The carbonylate anions follow the 18e rule. Their alkali metal salts are water soluble but they can be
crystallised with the large cations like R4N+, R4As+, etc.
yl
Properties: They are not generally stable and are readily oxidised in air. They may show the Bronsted
acidic property. Their reactions are discussed (in general) below and in Sec. 9.4.16. In the PMR spectra,
m
negative values of chemical shifts (8 = -5 to -15 ppm) are the characteristic features of the carbonyl
he
hydrides (cf Secs. 12.2.6, 12.2.19(J 1)).
(i) Bronsted basicity of carbonylates (cf Secs. 9.4.7E, 10.1, 10.4): The carbonylate anions may be
lc
protonated to produce their conjugate .acids called carbonyl hydrides. Their acidic property in terms of
the pKa values have been discussed in Secs. 9.4.7E, 10.1.
ea
The protonation of carbonylate anions may be done by the weak acids (HA), strong acids (H 30+),
water, alcohol, etc. depending 01) t~e proton accepting power of the carbonylate anions. Very strong
th
bases like [Re(CO)s]-, [Cr(CO)s12- etc. can be protonated by the simple protic solvents.
[Re(CO)s]- + H 20 ~ [HRe(CO)s] + OH-, pKa of [HRe(CO)s] ::::: 14
e/
[Cr(CO)5]2- + MeOH ~ [HCr(CO)s]- + MeO-

t.m
The Bronsted acid strength of the carbonyl hydrides depends on the relative stabilities of the
conjugate bases, i.e. [CO(CO)4]-' [Re(CO)s]-, etc. through the charge delocalisation by the 1t-acidity
of the CO groups. Obviously, presence of the weaker n-acid ligands like PPh 3 reduces the acid strength.
These are discussed in Secs. 9~4. 7E, 10.1.
e
Protonation of the strongly basic carbonylate [Cr(CO)4]2- by NH4CI + NH 3(l) leads to a dinuclear
er
species with the bridging hydride ligands.

H
k
lic
(ii) Reactions leading to, metal-carbon bond formation (cf. Sec. 10.4): Carbonylates as the
C
nucleophiles can attack on RX or RCOX to produce the metal-carbon bond.

·- :
Use of Collman's Reagent Na2[Fe(CO)4] (called Transition Metal

Grignard Reagent) in Organic Synthesis
(J.P. Collman, Ace. Chern. Res., 1, 136 (1968»
_H+--.~ [HFe(CO}4r(tbp)
2
[Fe(CO}J -(Td) +
__
ry
AiCH~O ~ RC0 H 2 H+
~ A-H
/ , . - - -...
ra
/6:~
R'-X
A-C -Fe(CO)4l- • co . [A-Fe(CO)4l ------+A-C-A'
ib
[ J (insertion)
I1
o 1x, (tbp, R in axial

position) 0
II
yl
H2 0
\ ° 2
, H20 ~ A-CO H
2
m
A-C-X ~ AC0 2 H
11 '",---R_'O_H_-+ [HFe(CO}4] (Hydride donor)
0 - ~ ACOOA'
he
I'-------.;;;...-..
R/NH2
ACONHA'
~
I +RX
~ AH + [XFe(CO)4r
- - -..
+ ACOCI
lc 10-.- --+ ACHO + [CIFe(CO)4r
ea
[CO(CO)4]- + RX ~ [R-CO(CO)4] + X-; [CO(CO)4]- + SiH3I ~ [H 3Si-Co(CO)]4 + 1-
~- CO(CO)4]
th
[R -CO(CO)4J +co )[ R - R'OH) RCOOR' + [HCO(CO)4]

e/
[Mn(CO)s]- + CH 2= CH-CH2-CI ~ [(OC)sMn-CH2CH = CH 2] + CI-

t.m
[HCO(CO)4] + R - CH=CH 2 ~ [RCH 2 CH 2 - CO(CO)4]' (ef Sec. 10.13.4)

(iii) Reactions leading to metal-metal bond formation: These are illustrated below.
[Fe(CO)4]2- + Hg 2+ ~ [FeHg(CO)4]; [Fe(CO)4]2- + 2Ph3PAuCI ~ [(Ph3PAu)2Fe(CO)4] + 2CI-
e
[Mn(CO)s]- + Ph 3PAuCI --7 [Ph 3PAuMn(CO)s] + CI-

er
[MnBr(CO)s] + [CO(CO)4]- ~ [(OC)sMnCo(CO)4] + Br-

H
[Mn(CO)s]- + [ReBr(CO)s] ~ [(OC)sRe-Mn(CO)s] + Br-

(iv) Anionic hydrido carbonyls as the hydride donors: Neutral carbonyl hydrides can show the
k
protonic hydrogens depending on their pKa values. But many anionic hydrido carbonyls show the
hydridic hydrogens and they can act as the hydride donors.
lic
[(11 5- CsHs)Mo(CO)3H] + CH 2N2 ~ [(l1S-CsHs)Mo(CO)3CH3] + N2

[(l1S-CsHs)Mo(CO)3H] + CCl4 ~ [(l1s-CsHs)Mo(CO)3CI] + CHCl3
C
[HCr(CO)s]- + RCOCI~[ Cr(CO)sCI]- + RCH

II
o
[HFe(CO)4]- +RX~[XFe(CO)4]-+RH
Because of the presence of hydridic hydrogens, sometimes they may act as the powerful reduc-
ing agents. In fact, in presence of acetic acid, [HCr(CO)s]- can reduce aldehyde (RCHO) to
primary alcohol.
RCHO + [HCr(CO)s]- + AcOH ~ RCH 20H + [(AcO)Cr(CO)s]-
[Co 2(CO)s] acts as a catalyst in the conversion of alkenes to aldehydes by CO and H 2. Here, it
is believed that the carbonyl hydride [HCo(CO)3] (16e-species) produced is the active species (cf
Sec. 10.13.4).
9.4.18 Carbonyl Halides: Synthesis, Structure and Properties

Synthesis: The reactions leading to the synthesis of carbonyl halides have been discussed in Sec. 9.4.7(F)
ry
Structure: These are given in Sec. 9.4.7(F).
Properties: They generally form the yellow or white crystals soluble in organic solvents. In general,
ra
the carbonyl halides [Mx(CO)yX z] follow the 18e rule though there are some exceptions e.g. [Rh(CO)2Cl]2
and trans-[Ir(CO)Cl(PPh 3)2] (Vaska's complex) follow the 16e rule. The reasons for obeying the 16e
ib
electron rule have been already discussed in Secs. 9.3 (Vol. 6), 12.8.5 (Vol. 3).
yl
Stability: The important observations are: (i) Pd, Pt, Cu, Cu, Au, etc. generally do not form the stable
metal carbonyls but they form the fairly stable carbonyl halides (stability order: Cl-) Br-) 1-); (ii) for
m
the common metals forming the stable carbonyls, the stability order for the carbonyl halides is: 1-) Br-
) CI-; (iii) [Ni(CO)4] is stable but [Ni(CO)3X]- (X = CI, Br) is unstable; [PdII CCO)CI 2]n is somewhat
he
stable; [Ptll(CO)2CI2] and [PtX 3(CO)]- are quite stable.
These can be rationalised in terms of the metal-carbonyl bonding. The halides are the a-bonding
lc
ligands and they are the electron withdrawing ligands. Consequently, they disfavour the metal ~ CO
ea
n-back bonding and destabilise the compounds like [Ni(CO)3X]-, [Ni(CO)2X2]2- for which the stability
mainly depends on the efficiency of the metal ~ CO n-back bonding. On the other hand, for the metals
like Pt, Au, etc. reluctant to participate in metal ~ CO n-back bonding due to their higher electronegativity
th
and higher effective nuclear charge, stability of such carbonyls mainly depends on the M ~ CO
a-bond. It is favoured when, the metal centre is coordinated with the electron withdrawing a-bonding
e/
ligands like halides.

t.m
[M(CO)L)], [M(CO)2L2], etc. (M = Pd, Pt; L = PPh 3) are known to exist. It happens so, because PPh3
is a good a-donor ligand but is a weak 1t-acceptor ligand. Probably in such cases, the favoured
M ~ CO 1t-bonding stabilises the compounds. Because of the same ground, [Co(CO)4I] is unstable
but [Co(CO)3I(PPh3)] is stable (cf Fig. 9.4.11.5 and competive n-bonding).
e
Chemical reactions: Some representative chemical reactions of carbonyl halides are given below.
er
[CO(CO)4]- + [MnBr(CO)s] ~ [(OC)5Mn-Co(CO)4] + Br-; (nucleophilic attack by carbonylate

anion on Mn)
H
[Fe(CO)4I2] + 2PPh 3 ~ [Fe(CO)2I2(PPh3)2] + 2CO; (CO can be also substituted by py).

[Mn(CO)4 I J + 2py~2[ Mn(CO)4I(py)] :;~~) 2[ Mn(CO)3I(PY)2]
k
2
Reactivities of Vaska's Compound have been discussed later.
lic
Solubility: They are generally soluble in organic solvents but they are decomposed by water.
[Fe(CO)4I2] + 6H 20 ~ [Fe(OH 2)6]I 2 + 4CO.
C
9.5 OTHER IMPORTANT 1t-ACID LIGANDS AND THEIR GENERAL BEHAVIOUR (cf. Fig.
10.7.8.1, Vol. 2)
(a) Pi-acid ligands isoelectronic with CO: Coordinating behaviour of the potentialn-acid ligand CO
has been discussed in detail in Sec. 9.4 and Chapter 10, Vol. 2. The important n-acid ligands isoelectronic
with CO are given below according to their n-acceptor strength.
(:C==N:)- ( : N==N:(:C==NR( :C==O: «(: N==O)+
This order has been determined from the knowledge of shifting of vco when CO and the other
ligand (say X) are placed in trans-positions in a particular complex. The two trans-axial ligands, i.e.
X and CO will compete for the same filled two metal d-orbitals for n-bonding (cf. Fig. 9.4.11.5). If X
is a stronger n-acceptor ligand (compared to CO) then less d-electron cloud will be pushed into the
vacant n* -MO of CO, i.e. veo will be relatively higher. On the other hand, if X is a poorer n-acceptor
ligand than CO, then veo will be relatively less. The isomer shift (MB spectra) of Fe-complexes for
different n-acceptor ligands can also determine their n-acid strength (cf. Sec. 12.4.7).
Anionic CN- (the weakest one in the series) acts as a very poor n-electron acceptor ligand because
ry
it is already electron rich. Compared to CO, the weaker n-acceptor property of CN- is also partly due
to the less electronegativity of N (compared to that of 0). In fact, CN- may undergo complexation even
ra
with the fairly high oxidation states of metals (e.g. Fe 3+, Cr3+, C0 3+, etc.) because it can act as a very
good a-donor ligand and as a poor n-acid ligand.
ib
yl
Special properties of CN-(cf. Sec. 9.7)
m
• It is a strong field ligand (i.e. high crystal field splitting power) when coordinating through the
C-end.
he
• Showing a good nephelauxetic effect.
• Capable of stabilising both the low and high oxidation states of metals.
lc
• Because of its anionic charge, it is a good a-donor ligand but a poor n-acceptor ligand.
a-donor strength sequence: CN-) RNC ) NO+ -- CO
ea
• It is a soft ligand (specially when bound through the C-end) because of its high polarisability
(anionic nature and enriched with the n-electron cloud)
th
• It can act as an ambidentate ligand.

• It can act as a bridging ligand.
e/
n-Acceptor series (approximate order)

t.m
NO+ ) CO, RNC, PF3 ) PCI 3, C 2H4, P(OPh)3) P(OEt)3) C 2H 2 ) P(SR)3 ) PPh3 ) PR 3 ) R 2S ) RCN
NO+ (strongest one in the series) acts as a very good n-acceptor ligand because it is already electron
e
deficient. NO+ generally is well known to stabilise the low oxidation states of metals because of its
er
good n-acceptor properties.

Complexing behaviour of these n-acid ligands will be discussed separately.
H
(b) Site preference of the n-acid ligands: Relative n-bonding efficiency of the ligands can direct
their site preference in the geometries like trigonal bipyramidal (tbp) having the nonequivalent sites.
k
In a tbp geometry, the n-back bonding is favoured when the ligand is placed in the equatorial position.
Thus, the better n-acid ligands tend to occupy the equatorial positions while the weaker n-acid
lic
ligands are pushed into the axial positions of a trigonal bipyramidal geometry. In this considera-
tion, the competing n-acid ligands have been considered to produce the comparable steric effects. It is
C
illustrated in the following two examples having the tbp geometry.

[Mn(CO)4(NO)] (NO as NO+ at the equatorial position)
[Fe(CN)(CO)4]- (CN- at the axial position).
The n-acceptor strength of the involved competing ligands is:
NO+) CO » CN-
This is why, the stronger n-acid ligands like NO+, CO occupy the equatorial positions while
CN-, a very weak n-acceptor ligand (mainly because of its anionic character) occupies the axial posi-
tion keeping the equatorial positions reserved for the better n-acid ligands like CO.
(c) 8 2 as a 1t-acid ligand': Dihydrogen (H 2) can act as a n-acid ligand and it will be discussed later.
(d) PR3 as a n-acid ligand: Pi-acceptor property runs as: CO ~ PF3 ) PCl 3 ~ P(OAr)3 ) P(OR)3 )
PAr3) PR 3, PH3 (R = alkyl group: Ar = aryl group)
The n-acidity of P(III)-ligands depends on the bulkiness and electronegativity of the substituents.
These aspects will be discussed later on (cf Sec. 9.10).
The n-acceptor property of PF3is more or less comparable to that of CO. Now it has been suggested
ry
that not the 3d-orbital of phosphorus but the vacant P-F antibonding orbital is the n-acceptor
orbital. This P-F antibonding orbital is mainly constituted by the 3p-orbitals of P. Thus the 3d-orbital
ra
of P plays only a minor role (if at all) in the n-acceptance of PF3 (cf Fig. 10.7.8.1, Vol. 2).
ib
(e) S02 as a n-acid ligand: Generally the lone pair of S-atom is used for coordination but it can act
s(°
yl
as a good n-acceptor ligand because of its electronegative O-atoms. When the segment M - is
m
°
he
coplanar (i.e. planar 111_S02 and all the 4 atoms lie in a plane), it is believed that the lone pair on sulfur
is used for a-donation and the vacant n* -orbital of S02 participates in n-back bonding. The examples
lc
are: [Co(NO)(PPh3)2(S02)]; [RuCI(NH3)4(S02)]CI; [Ni(PPh3)2(S02)2], etc.
In some cases, e.g. [M(CO)CI(PPh 3)2(S02)] (M = Rh, Ir), [Pt(PH3)3(S02)], it has been found that the
ea
plane of S02 is tilted with respect to the M-S linkage. In such pyramidal M-S02 complexes, it is
believed that a-donation occurs from the electron-rich metal centre to sulfur (i.e. S02 acts here as a
th
Lewis acid).
°
S02 can act as a bidentate chelating ligand (i. e. side-on 11 2) where both the Sand sites are used
e/
for metal binding, but they occupy one coordination site. Actually, the S-O pi-electron cloud is used
for a-donation and the vacant n* -MO is used for n-acceptance. It is noted in the complexes like
t.m
[Mo(CO)3(phen)(112-S02)], [Mo(CO)2(PPh 3)2(PY)(112-S02)]' The different modes of coordination of

S02 are shown in Fig. 9.5.1.
e
er
()
H
M 8
~o
k
°
lic
8 as a a-donor; 802 as a sigma acceptor;

C
2
1t* of 802 as a 1t-acceptor 802 as a Lewis acid. Bidentate 11 ·S02; 802 as a
1
(Planar M-111.S02 configuration) (Pyramidal M-11 • S02 configuration) 1t-acceptor.
(cf. Coordinating behaviour
of C2 H4 , O2 , etc.)
Fig. 9.5.1 Different modes of coodination by S02- (The 1t-acceptor property of S02 is supported by the lowering of v so
values compared to those of free S02)-
Note: Depending on the conditions, S02 can bind also through the O-end as in FsSb-OSO (prob-
ably the only example). 80 2 can show both the Lewis acid and Lewis base properties depending on the
condition. These are discussed in Chapter 14, Vol. 3.
9.6 METAL NITROSYLS: METAL COMPLEXES WITH NITRIC OXIDE AS LIGANDS

9.6.1 Coordinating Behaviour of NO
In terms of molecular orbital energy diagram, NO and CO are very much similar. In NO, there is an
additional electron (compar~d to CO) and it is housed in an antibonding n-MO. It makes NO paramagnetic.
The MO-diagram of NO is shown in Fig. 9.6.1.1. It is evident that NO+ is isoelectronic with CO.
ry
(6a*) I a*(2Px) ,
ra
I ,
I ,
,/ n*(2py, z) \
ib
,',~~
I / , ,
yl
~s:=~// (2n*) ",
\\ ~ 2p ,
'~jiJ!:~~
m
\,
",\ n(2py, z) /,
i (1n) -+ '===1FL=/ "
he
\ I
\ a (2px) I
(Sa) \ 1~ I
25 (4a*)
...--.......----"
,, 1~
a*(2s)
,
'
lc
ea
a(2s) " 25
(3a) "1~ - - --....-~
th
15 (2a*) a*(1s)
1~ ,
" a(1S)", 15
e/
, --1+'---1
AOs (1a) , 1~ AOs
(N) (NO) (MOs) (0)
t.m
- - - - - -....~
(b)
(a)
Fig. 9.6.1.1 MO energy diagram of NO. (a) simple diagram (Considering no s-p mixing, no symmetry interaction);
e
(b) by considering the s-p mixing (see Sec. 9.11.2, Vol. 2).
er
NO as a terminal ligand can coordinate with the metal centre in two possible ways, i.e. linear
M-N-O and bent M-N-O (Fig. 9.6.1.2).
H
(A) Terminal linear M-N-O group (cf. Fig. 9.6.1.2a): In this mode, in terms ofVBT, N is in sp
hybridisation state. In this fashion, NO is considered to act as a 3e-donor ligand. In terms of MOT, the
k
unpaired electron present in the n*-MO of NO is first transferred to a singly occupied metaln-orbital
lic
followed by a-donation of a lone pair (from a nonbonding MO or weakly a-antibonding MO which is

the HOMO for NO+, cf. Fig. 9.6.1.1b) from the N-end. In terms of the simple MO diagram (Fig.
C
9.6.1.1a), the a-donation may occur from the deeply seated ais(i.e. antibonding orbital) but the experi-
mental findings do not support this view fully. Transfer of the unpaired electron from the n*-MO of NO
to the 1t-orbital of metal centre formally generates NO+ and causes 1e-reduction of the metal centre.
This 1e-reduction of the metal centre followed by the a-donation of the lone pair can explain the
3e-donor property of NO. This the NO+ species generated can act as a very good ft-acceptor ligand I
by using the vacant ft·-MO predominantly located on the N-end. The cationic charge in NO+ further
favours the electron flow from metal to NO+.
Transfer of the unpaired electron from the n* -MO of NO to the metal centre (causing the 1e reduction
of the metal centre) shortens the N-O bond length but n-acceptance in the n*-MO will elongate-the
N-O bond. Thus the two opposing factors are operating to determine_the vN-o stretching frequency.
Here it is assumed (as in the case of CO), the lone pair used by NO+ for a-donation is basically residing
in a nonbonding MO (cf Fig. 9.6.1.1 b) Le., a-donation does not remarkably influence the N-O bond
donor MO of NO+
ry
ra
ib
yl
m
n* acceptor orbital
donor d-orbital
he
(vacant in NO+)
of metal
(a) Linear M-N-O linkage
lc
Donor MO for NO+: 3anb i.e. HOMO of NO+ (cf. Fig. 9.6.1.1 b); or a;s (deeply seated)
(cf. Fig. 9.6.1.1 a) (not supported experimentally)
ea
th
e/
t.m
e
n*2 (singlet NO-) ~ M 1e-(sp 2) for neutral

NO (2c-2e bond)
er
or
n*1 (1e in neutral NO) ~ M
"-- ------------)
H
---------o
(b) Bent M - N, linkage.
k
lic
II
C
L ------------)
---------
(c) a-interactions in bridging nitrosyls; vacant n*-orbital can
receive electrons from the metal centre.
Fig. 9.6.1.2 Different possible modes of binding of NO as a terminal ligand (a, b) and as a bridging ligand (c).
length. But in reality, the lone pair used for a-donation resides in a weakly antibonding MO which is
the HOMO for NO+ (cf Fig. 9.6.1.1 b). Thus, the a-donation will strengthen the N-O bond. However,
this effect is of very low magnitude. In general, it has been found that when NO binds as NO+
(isoelectronic with CO) giving rise to the linear M-N-O linkage, v NO increases compared to that of
free NO (v NO = 1876 cm- I ). It may be noted that vNofor freeNO+ is 2300 cm- I . However, because of
n-acceptance by the metal-bound NO+, the stretching frequency becomes less than 2300 em-J•
ry
In general, for the nitrosyl complexes (having NO+ as the ligand), v NO should lie in the range: (NO+)
2300 em-I) VNO (in complex) ) 1876 cm- 1 (free NO). But experimentally, it has been found in the range
ra
1660-1900 cm- I for the linear M-N-O linkage. It indicates the strong 1t-acceptance by NO+. It may
be noted that the bond angle may not be always exactly 180 0 • Generally, it lies in the range, 165 - 180 0 •
ib
(B) Terminal bent M-N-O group (cf Fig. 9.6.1.2b): In this mode of binding, in terms ofVBT,
yl
N is in Sp2 hydridisation state. It can happen in two ways: NO binds as neutral NO; and NO binds as
NO-. In both the cases, in the M-N-O segment, there is a lone pair on N and it causes the bending
m
(cf. VSEPR) in the linkage. When NO binds as a neutral moiety, it may be considered to act as a
1e-donor ligand. The unpaired electron makes a covalent linkage with an unpaired electron of the metal
he
centre just like as in organic nitroso compounds (e.g. R ~ N= 0, etc.) or in nitrosylchloride
(CI-N= 0).
lc
When the metal centre is in low oxidation state and it is electron rich, one electron from the metal
ea
centre can be transferred to the n*-MO (or sp2-hybrid orbital in terms of VBT) of NO giving rise to
NO- which can act as a 2e-eJ-donor ligand. In this situation, first the metal centre experiences le-
oxidation and overall NO acts as a Ie-donor ligand. In the formation of NO- due to the placement of
th
an additional electron in the n* -MO, the N-O bond lengtli should increase i.e. VNO will be less than
that of free NO (i.e. VNO: linear linkage) bent linkage).
e/
NO- is isoelectronic with dioxygen O2 and just like O2(cf Sec. 9.13), NO- makes a bent M-N-O
t.m
linkage. In fact, coordinating behaviour of NO- can be understood in terms of the bent M-O-O
linkage formed in the dioxygen adduct. In the bent M-N-O linkage, one of the n*-MO (i.e.SOMO)
o(NO- makes a a-type interaction with the metal orbital while the other n*-MO (i.e.SOMO) makes a
weak n-type interaction. Thus, degeneracy of the n* -MOs (i.e. SOMOs) of NO- is lost (Fig. 9.6.1.3).
e
Consequently, triplet NO-becomes singlet NO-. The electron pair in the n*-MO (i.e.HOMO) of singlet
er
NO- is used for a-donation and the vacant n*-MO (i.e. LUMO) of singlet NO- may accept the electron
from the metal centre. But the 1t-acceptance property of NO- is very poor because of its anionic
H
character. The details of coordinating behaviour of NO- (isoelectronic with O 2) are given in Sec. 9.13.
" LUMO
k
"
""
lic
""" P = pairing
-4- -+-
Bent mode of """ energy ~E > P
~~O~~i~~l~~ _.~~----------------
C
,,
n* MOs
,,
i.e. SOMOs
,,
,,
of NO- (triplet) ,,
HOMO
(Singlet NO-)
Fig. 9.6.1.3 Generation of singlet NO- (to act as a n-acid ligand) from triplet NO- in making the M-N-O bent linkage
(cf. Sec. 9.13).
Here it should be mentioned that in the bent M-N-O bond, it is very often difficult to identify the
chemical state of bound NO (whether neutral NO or NO-).
Thus we may conclude that when NO makes a linear M-N-O linkage, NO acts as a 3e-donor
ligand i.e. NO remains as NO+. On the other hand, when NO makes an angular M-N-O linkage, NO
acts as a Ie donor ligand. It may happen when NO remains as NO-. It is worth mentioning that both
NO+ and NO- act as the 2e-cr-donor ligands but NO+ is a strong n-acceptor ligand.
ry
Obviously, NO- is a relatively weaker n-acceptor ligand because of its anionic character though the
singlet NO- possess a suitable vacant n*-MO for n-acceptance. Here, it is worth mentioning that
ra
between the isolectronic singlet species, NO- and O2, the neutral species (i.e. O2) is a better n-acceptor
ligand (cf effect of charge and electronegativity).
ib
Here it may be mentioned that the terminal CO group always produces the linear M-C-O segment
yl
where CO acts as a 2e-donor ligand. CO can never make the bent M-C-O bond.
m
Bent and linear M-N-O linkage in terms of MOT
he
In explaining the linear linkage, 1e reduction of the metal centre by NO and then coordination by
the x-acid ligand NO+ (isoelectronic with CO) have been considered. This simple consideration
makes a good analogy with the bonding in metal carbonyls. On the other hand, in explaining the
lc
bent linkage, reduction of NO to NO- by the metal centre followed by the a-donation from
ea
singlet NO- and very weak x-acceptance by singlet NO- have been considered (cf coordinating
behaviour of O 2 and NO-; both of them make the bent linkage). However the linear and bent
M-N-O linkage formation can be understood as discussed below.
th
In terms of MOT the total complex, in the linear mode of coordination, because of the presence of
e/
vacant low-lying metal based MOs, the electrons are placed there and one lone pair is housed in
a nonbonding MO predominantly enriched with the character of metal-orbital. Thus apparently,
t.m
NO acts as a 3e-donor ligand. When such low-lying vacant metal-based MOs are already filled in,
the electrons are placed in the MOs predominantly enriched with the character of nitrogen orbitals.
In such cases, NO apparently acts as a Ie-donor ligand and one lone pair is housed in a nobonding
MO which is predominantly enriched with the character of nitrogen orbital. If the ~ectron
e
pair is to be used for n-donation (i.e. to act as a 3e donor ligand) to the metal, the M - N - 0
er
angle should open towards 180°. This is why, in the bent M - N - 0 linkage, the metal-ligand
H
n-bonding is inefficient.
This lone pair is housed in a MO enriched with the character of nitrogen.
_n
k
•~ This lone pair is housed in a MO

.r
lic
+ enriched with the character of

4 .. M====N ====0 ~ M-N nitrogen orbital.
~
C
Linear, sp-N
o
Bent, sp2-N
(cf.
o
M- C
0+
== 0 ~ M= C= 0; Linear, sp-C)
(C) NO as a bridging ligand (cf Fig. 9.6.1.2c): Just like the CO group, NO group can also act as
a bridging ligand. It can bridge as J.!2-NO and J.!3-NO. The intermolecular transfer of NO between two
complexes indirectly supports the formation of a bridged binuclear intermediate having J.!2-NO.
[CoCl(PPh))J + [Rh (NO)(PPh) ))J ~ [Co(NO)(PPh))J + [RhCl(PPh)))J
Both the symmetric and asymmetric bridges are known. Examples of complexes having the bridg-
ing NO groups are given in Fig. 9.6.1.4.
(1l5-Cp)
-175°
0", I /0
~2 ~#o N - - M n - - N f.!2-NO
('15_CP)~ / ~ ~~ . Il3-
NO
~l~ I (v NO = 1543, 1480 cm-
1
)
ry
/cr -860 cr~
-:::p ~ Mn~ ~Mn
ra
N
('1 5- Cp) / ~250pm/ ~
o (J.!2- NO ) II (1l5-Cp) ~ / (1l5-Cp)
ib
Cr- - - Cr = 265 pm N
o
I (v NO for J.!3-NO = 1328 cm- 1)
yl
[{Cr(1l5-cp)(NO)}2(J.!2-NH2)(J.!2-NO)] o
[Mn 3(1l5-Cph(J.!2-NO)3(f.!3-NO)]
m
vNO (terminal) ~ 1672 cm- 1
vNO (bridging) ~ 1505 cm- 1 Mn 3 ~ equilateral triangle
he
Fig. 9.6.1.4 Examples of complexes bearing the bridging NO groups
VNO: terminal-NO) J.Lr NO ) J.l3- NO; (cf. VCO)
lc
(D) Identification of the mode of binding of NO from VNO (see Sec. 12.1.17): It has been already
argued that in the linear terminal M-N-O linkage, NO remains as NO+ while in the bent tenninal
ea
M-N-O linkage, NO remains as NO-. Both NO+ and NO- act as the 2e-(J'-donor ligands but NO+ is
a strong n-acceptor ligand while NO- is a very weak n-acceptor ligand. Obviously, NO+ is a very poor
th
(J'-donor. From the knowledge of bond-order in the N-O linkage, we have:

(~ (~ (~
e/
VNO : v NO + 2300 em-I) ) v NO 1876 em-I) ) v NO - 1500 - 1600 em-I);

N-O (pm): 106 pm (NO+) ( 115 pm (NO) ( 120 pm (NO-)
t.m
Thus it is quite reasonable to expect that VNO should be higher in the linear M-N-O linkage
where NO exists as NO+ while it exists as NO- in the bent linkage. But the good n-acceptor property
of NO+ may complicate the interpretation. This n-bonding property largely depends on the nature of
e
the metal centre and the properties of the other ligands. Here it should be mentioned that for the bent
er
M-N-O linkage, the n-donor and n-acceptor properties of NO- are not expressed well. For an
efficient n-back donation from the metal centre, the M-N-O linkage should be at least approximately
H
linear. Generally, the following observations can help us to identify the bent or linear M-N-O
linkage.
k
-..
M-N-O V N- O (em-I)
lic
ca. 170 - 180 0

- 1660 - 1900 cm- I
(i.e. linear)
C
ca. 120 - 140 0

- 1525 - 1680 cm- I
(i.e. bent)
Compared to that of the terminal NO group, the v NO is shifted towards the lower frequency for the
bridging NO (cf. veo for terminal and bridging CO).
VNO (fJ.3) (VNO (J..I.2) (VNO (terminal) (cf Fig. 9.6.1.4).
[cf Veo (113) ( Veo (112) ( veo (terminal)]
From the experimental observation, it has been found that v NO for JJ.2-NO covers the range 1480 -
1540 cm- I while for J.l.3-NO it lies in the range 1300-1340 em-I.
Table 9.6.1.1 Characterisation of the linear (approximately linear) and bent M-N-O linkages in terms
of VNO.
Complex M-N-O
[Co(diars)(NO)]2+ 179 0 1852
[Fe(mnth(NO)]- 180 0 1866
ry
(approximatel y
Na2[Fe(CN)s NO] ·2H 20 0 1938
178 linear)
176 0
ra
[RuH(NO)(PPh 3h] 1645
K 3 [Mn(CN)s(NO)]·2H 20 174 0 1700
ib
[Ir(CH 3 )I(NO)(PPh 3 h] 0 1525
[Ir(CO)CI(NO)(PPh 3 h]BF4 120 0
124 1680
yl
124 0 (Bent) 1611
[CoCI(enh(NO)]+
119 0
m
[Co(NH 3)5 (NO)f+ 1610
[RuCI(NOh(PPh 3h]+ 1780 (linear) 1845
{ 137 0 (bent)
he
1685
1800 (linear) 1842
{. 127 0 (bent) 1635
lc
ea
th
Maleonitriledithiolate, mnt
e/
Ligating behaviour of NO-and O2 (cf. Sec. 9.13 and Fig. 9.13.3)

t.m
Both NO- and O 2 (dioxygen) are isoelectronic and their MO-diagrams may be approximately taken
as the same. The n*-MOs are singly occupied (i.e. SOMOs) and in the ground state, they are
triplet. Both of them form the bent linkage, i. e.
e
M-N andM-O
er
'" o '" o
H
It will be shown (Sec. 9.13) that in this mode of binding, degeneracy of the n*-MOs will be lost
and the triplet species becomes singlet, i.e. the lower n* -MO becomes filled in while the upper
k
n* -MO remains vacant (cf. Fig. 9.6.1.3). The electron pair in the n* -MO (i.e. HOMO) of singlet
lic
O2 or NO- is a used for a-donation and the vacant n* -MO (i.e. LUMO) is used for n-acceptance
from the metal. But as a n-acceptor one, NO- is very much weak compared to O2 because NO-
C
is already negatively charged and N is less electronegative than O. In fact, singlet NO- is a much
weaker x-acid ligand than singlet O 2• Thus, singlet NO- is a much weaker field ligand
than singlet O 2 • Probably, this is why, complete spin pairing in the brown ring complex,
[FeIII (NO-)(OH2)s]2+ is not attained (cf. Sec. 9.13, Vol. 6 and Chapter 16, Vol. 3).
Ligating behaviour of NO+ and CO
Both NO+ and CO are the isoelectronic species and they are the good n-acceptor ligands (n-
acceptance property: NO+) CO). Their ligating properties and modes of coordination are very
much similar.
It has been noted that depending on the conditions, in the nitrosyl complexes, v NO can vary in the
range, 1000 - 2000 cm- I for the different modes of coordination by NO. For the carbonyl-nitrosyl
complexes where CO and NO+ strongly compete for 1t-acceptance from the same metal d-orbitals
(Fig. 9.4.11.5), v NO generally varies in the range, 1500 - 1900 cm- I . The competitive 1t-bonding be-
tween NO+ and CO reduces the metal~NO+ 1t-bonding.
ry
9.6.2 Factors Favouring the Linear and Bent M-N-O Linkage
The coordination by NO can make the following events.
ra
(x-1)+
==
ib
./ M~ N 0; linear M-N-O, sp (N); as NO+
yl
X
M ++ NO /'
m
(Ignoring the n-bOnding)""-
, ' " (x+ 1)+ ••
M - - N~ ; bent M-N-O, sp2 (N); as NO-
he
o
lc
It has been already pointed out that binding of NO as a neutral molecule is rarely found. But an
intermediate state of the two limiting states, i.e. NO+ and NO- may complicate the assignment of
ea
oxidation state of metal.
• When the M-N-O linkage is linear, it indicates the presence of NO+ (i.e. NO acts as a 3e donor
th
ligand). For this event to occur, the metal centre experiences a Ie-reduction. Obviously the
electron transfer from the 1t*-MO of NO to the metal1t-orbital is favoured if the metal centre is
e/
electron poor, reducible and other bound ligands are good 1t-acid ligands that can stabilise the
t.m
low oxidation state.

• When NO binds as NO- giving rise to the bent M-N-O linkage, (i.e. NO acts as a Ie donor),
the metal centre experiences a Ie-oxidation. It is favoured when the metal centre is oxidisable
and electron-rich. Presence of good a-donor ligands like NH3, H 20, etc. also favours the
e
situation.
er
It is evident that in the linear M-N-O linkage, NO acts as a 3e-donor ligand while in the bent
linkage, NO acts as a Ie-donor ligand. Consequently, the earlier transition metals with the low lying
H
vacant orbitals suitable for accepting more electrons from the ligand prefer the linear linkage. On the
other hand, the late members of the transition series having the filled low lying orbitals can
k
accommodate the ligands that donate fewer electrons. In fact, such metal centres prefer the bent
lic
M-N-O linkage.
• Bent or linear M-N-O linkage in terms of the orbital housing the lone pair: In the linear
C
linkage, N is sp-hybridised and the lone pair resides on the metal centre while in the bent linkage, the
lone pair resides on the sp2-hybridised N-centre.
--~,., .. 7
.
fr N
lo~e pair -. bond
pair repulSion
M ~9:
(
v
linear linkage, sp - N bent linkage, sfi2- N
Position ofthe lone-pair, in question, determines the mode ofcoordination by NO. If there is a low-
lying vacant metal-based MO, then the lone pair is placed in such a MO to give the linear linkage. It
happens so for the electron poor metal centres (i.e. early members of the transition series). Shifting of
the lone pair in a such metal based MO allows the N-centre to adopt the sp-hybridisation and to function
as a n-acceptor ligand.
When the metal-based low-lying MOs are already filled in as in the electron rich metal centres (i.e.
ry
late members of the transition series), the lone pair is forced to house in a nonbonding MO predomi-
nantly enriched with the character of nitrogen. It leads to a bent coordination mode. The repulsion
ra
caused by the N-based lone pair enforces the bending of the M-N-O linkage.
ib
Thus in the nitrosyl complexes, presence of NO+ and NO- are the two limiting situations. It is
reasonable to consider the presence of neutral NO as an intermediate situation. Depending on the
yl
condition, NO group in the nitrosyl complexes may exist as NO+, neutral NO or NO-. It indicates that
NO is a polarisable ligand. Sometimes, to accommodate a nucleophile, the linear coordination mode
m
(i.e. NO+) may change to the bent coordination mode (i.e. NO-).
he
~ Nu 0
~
M-N~O
.. ':Nu
l~
- - - - - - :. .
'" .. /
M-N (Associative path)
(18e)U .. lc
(18e)
ea
The above predictions have been experimentally verified in many cases (ef Table 9.6.1.1) and
illustrated in the following examples and other examples discussed in Sec. 9.6.8.
th
(i) Equilibrium between the two conformations having the linear and bent M-N-O linkage:
When the energy difference between the two different modes of ligation by NO is marginally
e/
small, they may remain in an equilibrium mixture. In [Ir(113 - C 3Hs)(NO)(PPh3)2]+ , when crystallised
t.m
with the suitable counterions from CH 3CN or CH 2Cl 2 solution, both the linear Ir - N - 0 and
bent Ir -N- 0 coordinations are noted. By using the suitable counter-anions, either the Iight-
brown isomer (with linear Ir-N-O) or the red-brown isomer (with bent Ir-N-O) can be
crystallised out.
e
(ii) Fluxional behaviour of [RuCI(NO)2(PPh 3)2]+: It contains both the linear and bent nitrosyl groups
er
and they can undergo exchange in solutions and this fluxionality can be followed by 15N-nmr
spectroscopy. This fluxionality indicates that the energy difference between the two modes of
H
coordination of NO is small.
k
lic
C
Ru-N ~ 174 pm (linear linkage)

Ru-N ~ 186 pm (bent linkage)
The smaller Ru-N distance in the linear Ru-N-O linkage supports the extensive n-bonding in
the Ru-N bond.
Favourable situations for the bent M-N-O linkage

The electron rich late members of the transition series in oxidisable states with the other strong 0-
donor ligands prefer the bent M-N-O linkage. The lone pair resides on N because of the
nonavailability of low-lying metal based vacant MO.
Favourable situations for the linear M-N-Q linkage
ry
The electron poor earlier members of the transition series in reducible oxidation states with the
other n-acid ligands prefer the linear M-N-O linkage. The lone pair resides not on nitrogen but
ra
in a low-lying metal-based nonbonding MO.
ib
(iii) Stereochemical control on the mode of M-N-O coordination: In terms of the 18e rule,
yl
[Co(diars)2(NO)]2+ (trigonal bipyramidal structure) is expected to have NO+ as the ligand (i.e. NO
acts as a 3e-donor ligand). The 18e-count is: 7 + 3 + 4 x 2 = 18. In this trigonal bipyramidal
m
complex, the linear Co-N-O segment occupies one equatorial position. This equatorial
he
placement facilitates the 7t-bonding with NO+. When the complex is treated with SCN-, it
produces the octahedral complex, trans-[Co(diars)2(NCS)(NO)]+ in which NO acts as a Ie-donor
ligand to maintain the 18e configuration (i.e. 3e donor NO is converted into Ie donor NO to
lc
accommodate the additional 2e from SCN-). Thus in the octahedral product, the Co-N-O
ea
linkage is angular. This phenomenon has been descrived as the stereochemical control on the
coordination behaviour of NO.
th
[Co(diars)2(NO)]2+ + SCN- ~ trans-[Co(diars)2(NCS)(NO)]+

tbp, 18e, linear Co-N-O 0b' bent Co-N-O,
e/
(NO+ ligand) (NO- ligand)

t.m
e
SCN- ---.
er
As/I~AS
H
As II
k
C
= diars i.e., bidentate diarsine ligand;
lic
(
As IIS
C
diars= 0-
~AsMe2
AsMe 2
(iv) [Ir(CO)CI(NO)(PPh3 )2]+ vs. [RuCI(NO)2(PPh3 )2]+: Both the complexes are isoelectronic
but possessing different modes of M-N-O coordination. When the Vaska's complex,
[Ir(CO)CI(PPh 3)2] is treated with NO+PF 6- or NO+BF4, the square pyramidal complex
[Ir(CO)CI(NO)(PPh3)2]+ having the bent Ir-N-O segment (-124°) in the apical position is
produced.
[Co(CO)(NO)(PCl xPh 3- x)2] (X =0, 1, 2, 3): VNO and veo

For the given complex, with the increase of value of x, both v NO and v eo have been found to
increase from 1957 to 2045 cm- 1 and from 1715 to 1793 cm- 1 respectively.
vco(cm- 1): 1957(x = 0), 1987(x = 1),2024(x = 2), 2045 (x = 3)
ry
vNO(cm- 1 ): 1715(x = 0), 1747(x = 1), 1772(x = 2), 1793(x = 3)
ra
With the increase of the number of electronegative chlorine substituents on the phosphine ligand,
its a-donor property decreases but n-acceptor property increases. Consequently, with the increase
ib
of the value of x, the d(CO) ~ n*-MO(CO, NO) n-back bonding becomes disfavoured (cf. Fig.
yl
9.4.11.5) and it makes veo and VNO higher.
m
[lr(CO)CI(PPh 3)2] + NO+ BF4- ~ [lr III (CO)CI(NO)(PPh 3)2]+BF4- ; oxidative addition
he
From the starting Vaska's complex of Ir(l) (J8), a complex of Ir(lll) is prduced through the
transfer of 2e from Ir(l) to NO+ to generate NO- which subsequently binds in a bent mode. This
lc
mode of coordination is attained due to the oxidisable nature of Ir(l) (J8). In fact, Ir(l) easily
experiences an oxidative addition under suitable conditions.
ea
Interestingly, in the isoelectronic [RuCI(NO)2(PPh 3 )2]+ species, both NO+ (i.e. linear
M-N-O bond) and NO- (i.e. bent M-N-O bond) are present. Both Ir(lll) and Ru(ll) are
th
characterised by the tf configuration but Ir(lll) is more reluctant in showing the metal ~ ligand
n-donation because of its more effective positive charge. Besides this, in the heavier transition
e/
metals, the enhanced electronegativity disfavours the said n-back bonding to some extent. When
the metal --+ ligand 1t-bonding is disfavoured, NO binds in a bent mode. This is why, in the
t.m
given Ir(lll) complex, the Ir-N-O linkage is angular. Compared to the Ir(lll) complex, in the
Ru(ll) complex, the said n-back bonding can occur better. This is why, it probably allows both
the linear and bent modes of coordination by NO.
e
(v) [Co(diars)2(NCS)(NO)]+ vs. [Cr(CN)s(NO)]3-: We have already discussed that in the Co-com-
er
plex, the Co-N-O segment is bent but in the given Cr-complex, the Cr-N-O segment is
linear. It is reasonable because the electron poor early members of the transition series gen-
H
erally prefer the linear M-N-O linkage, i.e. binding of NO as a 3e-donor ligand. Moreover,
presence of 5 CN- groups (acting as the 1t-acid ligands) in the Cr-complex, favours the lower
k
oxidation state of metal and it favours binding of NO as NO+.

lic
(vi) Vaska's complex of Ir(I): We have already mentioned this. In this complex, Ir(l) (tJ8) is quite
oxidisable and this complex binds NO as NO-
r,(
C
[Ir'(CO)Cl (PPh 3 )2 ]_N_O+_P_F6---+{Ir IIl (CO)Cl (NO) (PPh 3 )2 cf· oxidative addition)
(M-N-Obent)
In fact, Vaska's complex of Ir(l) readily undergoes oxidative addition giving rise to the Ir(lll)
complex. In this regard, binding of dioxygen and dihydrogen to the complex may be recalled.
(vii) [Co(NH3)s(NO)]2+: Presence of the good a-donor ligands (i.e. NH 3) at the oxidisable Co(ll)
centre prefers the binding of NO as NO-, i.e. the complex is [CO III (NH 3)5(NO-)]2+. A similar
situation prevails in the brown ring complex, [Fe III (NO-)(OH 2)5]2+ (Ref. [norge Chern. 41, 4-10,
2002).
(viii) [Cr(CN)s(NO)]3-: Presence of the 1t-acceptor ligands (i.e. CN-) at the electron-poor early transition
metal centre favours the presence of NO+, i.e. the complex is [CrI (CN)5(NO+)]3-. The similar
situation prevails in nitroprusside ion, [Fe II (CN)5(NO+)]2-.
(ix) Brown ring complex, [Fe III (NO-)(OH2)s]2+ vs. nitroprusside ion [Fe(CN)s(NO)]2-: These have
been discussed in detail in Sec. 9.6.8, Vol. 6 and in Chapter 16, Vol. 3.
ry
9.6.3 Chemical Distinction between the Linear and Bent M-N-O Linkages
ra
In the linear M-N-O linkage, presence of the electron deficient species NO+ allows the nucleophilic
attack on N while in the bent M-N-O linkage, presence of the electron rich NO- allows the
ib
electrophilic attack on N.
In nitropruside, [Fe(CN)5(NO)]2-, existence of NO+ (i.e. linear Fe-N-O linkage) is supported by
yl
the fact that the nucleophiles like -OH, S2-, etc. can attack on N.
m
/0 l3- _
NO~
he
-OH 2 .. (NC)5 Fe _ N" OH 2 • (NC)sFe _ 4-
" (-H 20)

OH 2
lc
ea
th
e/
(Characteristic violet colour,

t.m
detection of sulphide)
Other examples of nucleophilic attack on N of coordinated NO+ are:

e
er
H
k
lic
C
9.6.4 Comparison of the Linear M-C-O and M-N-O Bonds

Under the comparable condition, the M-CO and M-NO (linear) bonds appear to be equally strong.
It is evidenced by the fact: the M-C and M-N bond lengths differ by a constant amount of about 7
pm. This difference arises from the difference in the covalent radii of C and N. However, ligand
substitution on the mixed carbonyl nitrosyls usually leads to the substitution of CO rather than NO. It
may be due to the kinetic reasons (cf Sec. 9.6.6 and Chapter 10).
9.6.5 Relative Instability of the Pure Nitrosyl Complexes: Requirement of Electron

Withdrawing Pi-acid Ligands to Stabilise the Nitrosyl Complexes
Pure carbonyls are well documented but pure nitrosyls are rarely known. In fact, [Fe(NO)4] and [Cr(NO)4]
are probably the only examples of pure nitrosyls. Generally, nitrosyl ligands are found in the mixed
ligand complexes e.g. carbonyl nitrosyls. CO is a good 1t-acid ligand to introduce the double bonded
character in the M-C bond. But NO can act as a 1t-acid ligand when it is NO+, i.e. binding of NO+ can
ry
introduce the double bonded character in the M-N bond.
ra
Stability of the carbonyls is attained through the introduction of the double bonded character in the
M-C bond and similarly stability of the nitrosyl complexes can be attained if the double bonded
ib
character in the M-N bond can be introduced. For this purpose, NO will have to act as a 3e donor
ligand to generate the linear M-N-O linkage. In this event, each linear M-N-O linkage will lower
yl
the oxidation state of the metal centre by one unit. If a metal centre contains all the ligands as the
linearly bound NO ligands, then there will be an excessive accumulation of negative charge on the
m
metal centre. But it is not a desirable situation. In the mixed ligand complexes (i.e. NO and other pi-
he
acid ligands like CO), such an undesirable situation can be avoided. In fact, presence of the other 1t-
acid ligands (e.g. CO, etc.) is quite essential because these 1t-acid ligands can withdraw the negative
charge accumulated on the metal centre (due to the 3e-donor property of NO which makes the linear
M-N-O linkage) to some extent.
lc
ea
Sometimes, the electron withdrawing groups like halides can also stabilise the nitrosyl compounds.
Such electronegative groups (e.g. halides) can take away (through the a-bond) the load of negative
th
charge developed on the metal centre due to the 3e-donor property of the NO.
In terms of elecron count, 3M-CO == 2M-NO (linear linkage) == 6e. Thus [Fe(CO)2(NO)2] and
e/
[Co(CO)3(NO)] are isoelectronic with [Ni(CO)4]. These are also isostructural. Similarly, [Fe(CO)2(NO)2]
is isoelectronic (but not isostructural) with [Fe(CO)s]. In the same way, [Cr(NO)4] and [V(CO)s(NO)]
t.m
are isoelectronic with [Cr(CO)6].

Here it should be mentioned that if the other ligands are basically the a-donor ligands, then NO may
not bind as NO+ but as NO- where the metal centre experiences an oxidation as in the brown ring
e
complex. In such events, NO acts as a Ie-donor and forms the bent M-N-O linkage.
er
Thus if total coordination number is satisfied by NO alone, then binding of NO as the 3e donor
ligands will give a high negative charge on the metal centre. If all the NO ligands bind as the Ie-donor
H
ligands then there will be an excessive accumulation of positive charge on the metal centre. Thus both
the situations are disfavoured. To avoid these unfavourable situations, even in pure nitrosyl com-
k
plexes, some NO ligands bind as the 3e donor ligands and some NO ligands bind as the Ie donor
lic
ligands. In fact, [Fe(NO)4] is actually [Fe(NO+)3(NO-)] which maintains the I8e configuration. Thus
[Fe(NO)4] is actually a mixed ligand complex. In [RuCl(NO)2(PPh3)2], one NO group exists as NO+
C
while the other NO group exists as NO-.

It has been already mentioned the requirement of the presence of other (electron withdrawing)
ligands in the nitrosyl complexes. The important types of mixed ligand complexes containing the
nitrosyl ligands are given below.
(i) Nitrosyl-carbonyls: [Co(CO)3(NO)], [Fe(CO)2(NO)2], [Mn(CO)4(NO)], [Mn(CO)(NO)3]' etc.
(ii) Nitrosyl-halides: [CoI(NO)2]b [FeI(NO)2]2' [Fe(NO)3X], Vaska's complex etc.
(iii) Nitrosyl cyanides: [Fe(CN)s(NO)]2-, [Ni(CN)3(NO)]2-, etc.
(iv) Nitrosyl-thio complexes, i.e. Roussin's Salts: [Fe(NO)2(SR)]2.
9.6.6 Difference in the Ligand Substitution Paths for the Carbonyls and Carbonyl-
Nitrosyls (ct. Chapter 10, Sec. 10.2)
Generally, the pure carbonyls adopt the dissociative path while the nitrosyl metal carbonyls adopt the
associative path. Let us illustrate for the following isoelectronic and isostructural species.
[Ni(CO)4]' [Fe(CO)2(NO)2] and [CO(CO)3NO]
ry
"-y------I \ v I
D- path, slower rate A-path, faster rate
-+~o ) [Ni(CO)3 (L)], D-path
ra
[Ni(CO)4]
[ Fe(CO)2(NO)2] -+c~ ) [Fe(CO)(NO)2 (L)], A-path
ib
[CO(CO)3 (NO)] _~LO ) [CO(CO)2 (NO)(L)], A-path
yl
m
(L = PR 3 )
Thus, the pure carbonyl like [Ni(CO)J reacts slowly in a D-path while the isoelectronic nitrosyl
he
carbonyls react relatively faster in an A-path.
There are two reasons to explain the difference in reactivity.
lc
(i) Effect of formal charge: By considering NO as NO+ in the complex, the oxidation states of the
isoelectronic species are: Fe(-II), Co(-I), Ni(O) in [Fe(CO)2(NO)2], [Co(CO)3(NO)] and [Ni(CO)4]
ea
respectively. Thus the positive charge increases as: Fe ( Co ( Ni. This is reflected in their veo
stretching frequencies. Higher positive charge on the metal centre will disfavour more the metal
th
~ CO n-back bonding, i.e. this n-back bonding efficiency will run as: Ni ( Co ( Fe and v eo runs
as : veo (Fe2-) ( veo (Co-) ( veo (Ni D).
e/
It is reasonable to assume that the M-CO bond strength is primarily determined by the metal ~ CO
n-back bonding. Thus the expected M-CO bond strength is:
t.m
Fe(-II)-CO) Co(-I)-CO) Ni(O)-CO.

This is why, the activation energy in the dissociative path (i.e. M-CO bond dissociation at the rds)
will be the highest for Fe(-II) and lowest for Ni(O). Thus the ease of D- and A-process will occur in the
e
sequence:
D-process: [Ni(CO)4] ) [Co(CO)3(NO)] ) [Fe(CO)2(NO)2]
er
A-process: [Fe(CO)2(NO)2] ) [Co(CO)3(NO)] ) [Ni(CO)4].

(ii) Electromeric effect of the coordinated NO group: It has been :Jready pointed out that the
H
coordinated NO group is highly polarisable. Depending on the condition, it may remain as NO+
or NO-. Generally, to maintain the EAN rule (i.e. I8e count), NO binds as a 3e-donor ligand
k
giving rise to the M-N-O linear linkage (i.e. present as NO+ which acts as a good 1t-acceptor
lic
ligand). But it can also act as a Ie-donor ligand giving rise to the M-N-O bent linkage (i.e.
presence of NO- which basically acts as a a-donor ligand).
C
The change in the mode of coordination, i.e. linear M-N-O (3e donor) to bent M-N-O (Ie
donor) can generate a vacant orbital on the metal centre with 16e count. This electromeric
change occurs in presence of an approaching nucleophile to assist the A-path.
L
M = N= 0 ~E-------:1~~
.... M-
..N~ o
I/" ;
~:L
M r==j'J=O --.....:J~~
I ..~o
M-N
(18e) (16e) (18e)U •• (A-path) (18e)
Such a path is not possible for the pure carbonyls.

(Note: Some organometallic compounds containing 116-C6H6' l1s-Cp, 113-allyl, etc. can also rear-
range from the 18e configuration to the 16e configuration to accommodate the nucleophile in an
associative path. This aspect has been discussed in Sec. 10.2.1).
9.6.7 Synthesis of Nitrosyl Carbonyls and Other Mixed Ligand Complexes Containing
the Nitrosyl Ligands
ry
Replacement of other ligands by NO gives the nitrosyl complexes. Sources of NO are:
Direct use of NO; NOCI; nitrosonium salts; nitrites; conc. HN0 3. etc.
ra
(i) Direct replacement by using NO:
[Fe(CO)s] + 2NO ~ [Fe(CO)2(NO)2] + 3CO
ib
(ef in terms of electron count: 3CO == 2NO).
yl
[Cr(CO)6] + 4NO ~ [Cr(NO)4] + 6CO
(ef [Cr(NO)4] is probably one example of the few pure nirosyls known).
m
[Mn(CO)sI] + 3NO ~ [Mn(CO)(NO)3] + 4CO + 1/2 12
(ef in terms of electron count: NO == CO + I, i.e. 3NO == 4CO + I)
he
[Fe(CN)6]3- + NO ~ [Fe(CN)s(NO)]2- + CN-; (ef replacement of CN- by NO+)
[C0 2(CO)g] + 2NO ~ 2[CO(CO)3NO] + 2CO
lc
(ii) Direct addition of NO to the coordinatively unsaturated complexes:
ea
[CoCI 2L 2] + NO----7[ CoCI 2L 2(NO)].
Disadvantages in using NO: Direct use of CO (in excess) for the carbonyl synthesis at high
th
temperatures and pressures does not create any problem but direct use of NO (in excess) at high
temperatures and pressures may lead to an unfavourable oxidation and the complex may undergo
e/
decomposition under the experimental condition. This is why, use of nitrites, nitrosyl chloride,
nitrosonium salt etc. gives the safer route of synthesis of nitrosyl complexes.
t.m
(iii) Use of nitrite or nitrous acid:

[CO(CO)4]- +HN02 +H+ ----7[Co(CO)3(NO)]+CO+H 20
e
[CO(CO)4]- +N0 2 +2C0 2 + H 20----7[Co(CO)3(NO)] + 2HC0 3 +Co.

er
[Fe(CN)6]4- +N0 2 +H 20----7[Fe(CN)s(NO)]2- +20H- +CN-.

(iv) Use of nitrosonium salts (e.g. NOBF4, NOPF6, NOHS0 4 etc.):
H
[(OC)sW-SnMe3]- + NO+ ~ [(ON)(OC)4W-SnMe3] + CO

[(l1s-CsHs)Re(CO)3] + NO+ ~ [(l1s-CsHs)Re(CO)2NO]+ + CO
k
[Rh(CNR)4]+ + NO+ ~ [Rh(CNR)4(NO)]2+

lic
[lr(CO)2L2] + NO+ ~ [lr(CO)L 2(NO)]+ + CO

C
[lr(CO)CI(PPh 3 )2] + NO+ ~ [lr(CO)CI(NO)(PPh 3 )2]+

(v) Use of NOel:
[Ni(PPh 3 )4] + NOCI ~ [Ni(CI)(NO)(PPh 3)2] + 2PPh 3
[Mn(CO)s]- + NOCI ~ [Mn(CO)4(NO)] + CI- + CO
(vi) Use of conc. UN0 3 ([1 2HN0 3 ~ NO+ + NO:;- + ~02 + H 20).
[Fe (CN)6 J4- _Co_nc_',H_N_O.~-----+)[Fe (CN)5 (NO) J2-

(nitroprusside)
(vii) Use of NH 2 0H in basic solution (for the cyanido-nitrosyl complexes):

2NH 20H ~NH 3 + H20 + [NOH] (= H+ + NO-).
[Ni(CN)4]2- + 2NH 20H + MOH ~ [Ni(CN)3(NO)]2- + NH 3 + 2H 20 + MCN
[Cr(CN)6]3- + 2NH 20H + MOH ~ [Cr(CN)s(NO)]3- + NH 3 + 2H 20 + MCN
9.6.8 Some Representative Nitrosyl Complexes of Importance
ry
(A) Roussin's salt: These are the nitrosyl-thio complexes of Fe(II) bearing the Fe-Fe interaction.
ra
Roussin's red salts are: M2[Fe2(NO)4S2], M+ = Na+, K+ or NHt. The corresponding esters are:
[Fe(NO)2(SR)]2 where R = C 2Hs, C6H s, etc. Roussin's black salts are: M[Fe4(NO)7S3] where M+ = Na+,
ib
K+, Rb+, Cs+, NH4+, etc. The Roussin's salts have got the biological relevance with ferredoxin (i.e. Fe-
S proteins). Roussin's black salts show the antibacterial activity. Esters of red salt, i.e. [Fe2(NO)4(SR)2]
yl
have been found to promote the activity of certain carcinogens.
m
Roussin's red salts can be prepared by allowing the iron nitrosyl halide to react with the alkali sulfide.
~2~I )K2[Fe(NOhSJ2~[Fe(NOMSR)J2
he
[FeI(NO)2J 2
Tpe ester can be obtained as follows:
[Fe(CO)2(NO)2] ~~~ )[Fe(NO)2(SR)]2

lc
ea
The red salt can also be prepared in the following route.
th
Suspension of FeS
e/
or Fe (II) -salt (in a passing of NO

>-----~)Roussin'sred salt.
solution of alkali
t.m
polysulphide).
The Roussin's red salts are less stable than the black salt. In fact, on standing, the red salt gradually
transforms into the black salt which on boiling with alkali regenerates the red salt.
e
The structure of [Fe(NO)2(SR)]2 is as follows:

er
H
k
; (Roussin's red salt)

lic
V I.
r
C
(Structure may be compared with that of 2Fe-2S ferredoxin)

The diamagnetic character is attained due to the Fe-Fe interaction. Each Fe-centre is in a dis-
torted tertrahedral geometry.
The structure of the black salt is complicated. The 4Fe-centres are at the corners of a pyramid.
Three triangular faces of the pyramid place one S-atom above each and the S-centre is linked with the
three Fe-centres (i.e. J.l3-S), In black salt also, there is an iron-iron interaction. Each Fe-centre is placed
in a distorted tetrahedral geometry (3S, 1N or 2S, 2N) and the remaining vacant coordination sites are
occupied by NO.
0\ Ft-
o l-
' :=~-- ;\'5<::s.,
~/t-
0
o : 'Fe~"
(-270 m)\ /
ry
s ---
"N
" Fe'«:----
: /
-- --- - - '-Fe
.\ / N ; (Roussinls black salt)
I I
ra
(-360 pm)
N N N
I
o
I I
ib
0 0
FebaSe •.•••• Fe baSe ~ 360 pm ; Fe baSe ...... Fe apex ~ 270 pm ;
yl
(ct. Fe - Fe single bond ~ 250 pm)
m
(B) Nitroprusside ion, i.e. [Fe(CN)s(NO)]2-: Sodium nitroprusside, Na2[Fe(CN)s(NO)], i.e. sodium
pentacyanidonitrosylferrate(II) is well known for its analytical use (detection of sulfide) and medical
he
use (to control the high blood pressure and to induce muscle relaxation).
Na2[Fe(CN)s(NO)] is prepared by heating K4[Fe(CN)6] with 30% HN0 3.
[Fe(CN)6]4- + 4H+ + N0 3- ----t [Fe(CN)s(NO)]2- + CO 2 + NHt. lc [ ) J ·2H 0
[ ( )J
ea
(i) boiling with 30% HNO)
K 4 Fe CN 6 ) Ruby-red crystals of Na 2 Fe (CN)s(NO 2
(ii) cooling to separate KN0 3
(iii) brown filtrate is neutralis~d
with Na 2CO)
th
Nitroprusside may be obtained also as follows:

e/
[Fe(CN)6]4- + N0 2- + H 20 ----t [Fe(CN)s(NO)]2- + CN- + 20H-

Nitroprusside gives the characteristic purple colour with sulfide in an alkaline condition.
t.m
[Fe(CN)s(NO)]2- + S2- ----t [Fe(CN)s(NOS)]4-

Here S2- makes a nucleophilic attack on the N-site of coordinated NO+.
With sulfite, it gives the rose-red coloration due to [Fe(CN)s(NOS0 3 ) ]4- formation. It is formed due
to the nucleophilic attack by S03 2- on the N-site of coordinated NO+, i.e.
e
er
SO ]4-
(NC)sFe-N(o 3
H
When [Fe(CN)s(NO)]2-- is treated with alkali, it gives the nitro-complex (again due to the nucle-
k
ophilic attack of OH- on N), i.e. [(NC)sFe(N0 2)]4-

lic
[Fe(CN)s(NO)]2- + 20H- ----t [Fc(CN)s(N0 2)]4- + H 20. "'-

Structural features of nitroprusside ion: Its diamagnetic character, almost linear Fe - N - 0
C
(::::: 178°) linkage, N-O ::::: 113 pm, (cf 115 pm in free NO), v NO ::::: 1940 cm- l (cf 1876 cm- l in free NO)
Fe(lI) ~ +NO
indicate the presence of NO+ (i.e. NO acts as a 3e donor ligand) and Fe(ll) (t2~)' i.e. the complex is
[Fe II (CN)5(NO+)]2-. In fact, presence 5CN- ligands acting as the n-acceptor ligands encourages NO to
act as a 3e-donor ligand. However, Mossbauer studies indicate that there is an appreciable extent of n-
delocalisation of electron cloud from the metal centre to the nitrosyl group and cyanido-groups.
(C) Brown-ring complex, i.e. [Fe(NO)(OH2)s]2+ (see Chapter 16, Vol. 3): This brown coloured com-
plex is formed during the detection of nitrate through ring test. In this test, freshly prepared FeS04
ry
solution is mixed with the solution containing nitrate in a test tube. Then conc. H2S04 is run down the
side of the test tube and the added acid forms the bottom layer. In presence of conc. H2S04, N0 3- reacts
ra
with Fe(ll) to generate NO which undergoes complexation with Fe(ll) to produce the brown complex
[Fe(NO)(OH 2)5]2+ that forms a ring at the interface of two layers of liquIds. If the mixture is heated, the
ib
brown clour disappears through the release of NO and the resultant solution contains Fe2(S04)3'
yl
N0 3- + 4H+ ~ NO + 2H 20 - 3e
Fe 2+ ~ Fe 3+ + e
m
i.e. N0 3- + 4H+ + 3Fe2+ ~ NO + 3Fe3+ + 2H 20
he
[Fe(OH 2)6]2+ + NO ~ [Fe(NO)(OH2)5]2+ (brown ring complex).
1 lc
Heating
ea
[Fe(OH 2)6]2+ + NO
The said brown ring complex is not very much stable. It decomposes gradually even on standing at
th
room temperature. It may be noted that N0 2- also gives the same test. For N0 2-, the brown ring complex
is produced even in presence of dil. H2S04
e/
i.e. N0 2- + dil. H 2S04 + Fe 2+ ~ brown ring complex

Structural and bonding aspects of the brown ring complex (cf. Rudi van Eldik et ai, Inorg. Chern.,
t.m
41,4-10,2002): The magnetic moment and ir-data are: Jleff::::: 3.9 B.M., VNO::::: 1750 - 1810 cm- I . The
magnetic moment indicates the presence of three unpaired electrons. This is why, it is assumed that in
the complex, NO exists as NO+ (i.e. NO acts as a 3e donor ligand) and during complexation, Fe 2+ is
e
reduced to Fe+ (dl-system, i.e. t2;ei in high spin state giving rise to three unpaired electrons). The ir-
data also support the presence of NO+ with an indication of electron flow from the metal to the n*-MO
er
of NO+ through the n-bonding (v NO for free NO+ = 2300 cm- I ).

But, such a low oxidation state of the metal centre (i.e. Fe+ 1) in presence of so many good (J-
H
donor ligands (i.e. 5H20) is called in question. In fact, Eldik et al has expressed (2002) an alternative
view mainly based on the Mossbauer and EPR data which cannot be explained by the composition,
k
[Fe+ I (NO+)(OH 2)5]2+ but by the composition [Fe+3(NO-)(OH 2)5]2+ where NO is argued to coordinate as
lic
NO- in an angular fashion, i.e. Fe - N . The 5 unpaired electrons of Fe 3+ (i.e. ~2ge;) undergo the
"0
C
antiferromagnetic coupling interactions with the two unpaired electrons of NO-. This antiferromagnetic
coupling interaction between the high spin Fe(lll) (S = 5/2) and NO- (S = 1) gives the spin quartet
ground state (S = 3/2). It explains the magnetic data. In [FelI(L)(NO)] (L = polyaminocarboxylates),
complexes, the bent Fe - N linkage is explained by the FellI - (NO)- interaction and the observed
"0
v N - O = 1777 cm- I (J. Am. Chern. Soc., 117, 715, 1995) for such complexes is close to VNO found for the
brown ring complex. In the antiferromagnetic coupling between Fe(lll) (S =5/2) and NO- (S = 1), some
electron cloud is shifted towards the metal centre. This explains the higher values of v NO compared to
that of free NO- (1500-1600 cm- I ). Thus, the ir-data of the brown ring complex can also be explained
by the FeIII-NO- composition involving the ligand to metal n-bonding and by comparing with the
reported ir-data for the other complexes having the FeIlI-(NO-) composition.
The bent Fe - N linkage in the brown ring complex can be best explained in terms of MOT
"'0
ry
(cf Fig. 9.13.3). It may be noted that NO- is isoelectronic with O2 which also binds in an angular
ra
fashion, i.e. M - 0 . In terms of the MO-diagram (Fig. 9.13.3), it can be shown that the interme-
"'0
ib
yl
diate spin state (i.e. placement of 7 electrons in 5 MOs constituted by three t 2g orbitals of Fe(II) and
two n*-MOs of NO) gives S = 3/2. The lower MOs which are filled in are enriched with the character
m
of n*-MOs of NO. It indicates the electron flow from the metal to NO explaining the
FeIII-(NO-) composition.
he
(D) Brown ring ion vs. Nitroprusside ion: Electronic control over the coordinating properties of
NO: The brown ring complex is argued (Inorg. Chern., 41, 4-10, 2002) to be constituted by FellI and
lc
NO-, i.e. [Fe IlI (NO-)(OH 2)s]2+ while nitroprusside complex is believed to be constituted by Fell and
NO+, i.e. [Fe ll (CN)s(NO+)]2-. Let us try to explain the cause behind the different modes of coordination
ea
of NO in these two cases in terms of the nature of the other ligands present in the coordination sphere.
In the nitroprusside complex, other remaining ligands (i.e. cyanides) are the 1t-acid ligands while in
th
the brown ring complex, other remaining ligands (i.e. aqua ligands) are the good a-donor ligands. The
n-acid CN- ligands favour the lower oxidation state and Fe(III) can be easily reduced to Fe(II). In other
e/
words, they favour the reduction of the metal centre by NO and disfavour the further oxidation of the
metal centre by NO. Thus, the CN-Iigands encourage NO to bind as a 3e-donor ligand through the
t.m
1e reduction of the metal centre and this reduced metal centre will eventually favour the metal ~ ligand
n-back bonding for NO+ and the existing n-acid ligands (i.e. 5 CN-). The a-donor H 20 ligands of the
brown ring complex, prefer the higher oxidation state of the metal centre (i.e. favouring the oxidation
e
of iron by NO) but disfavour the further reduction of iron. In fact, aqua-complex of Fe(II) is quite
er
oxidisable. Thus the aqua ligands encourage NO to bind as a Ie-donor ligand, i.e. as
NO-.
H
If the brown ring complex is taken as [FeI (NO+)(OH 2)s]2+, then it raises a valid question regarding
the stabilisation of Fe(I) in presence of so many a-donor aqua ligands.
k
The above two complexes illustrate the electronic control of the other ligands on the coordinating
lic
behaviour of NO.
Thus we can conclude:
C
• presence of a-donor ligands at the oxidisable metal centre prefers the coordination of NO as
NO- through the 1e oxidation of the metal centre by NO.
• presence of 1t-acceptor ligands at the reducible metal centre prefers the coordination of NO
as NO+ through the 1e reduction of the metal centre by NO.
The above conclusions are supported by many other experimental facts.
(i) In [Co(NH 3 )s(NO)]2+, NO exists as NO-, i.e. [CO III(NH 3 )s(NO-)]2+. Presence of five good
a-donor ligands (i.e. NH 3 ) at the oxidisable Co(II) centre prefers the binding of NO as NO-. The
observed v NO ::::: 1500 cm- I also supports this view. The present example is very much comparable
to the brown ring complex.
(ii) Vaska complex of Ir(I) (d8) is quite oxidisable and binds with NO+ as NO-
[Ir I(CO)(Cl)(PPh 3 )2 ] NO· PF6 ) [Ir

III
(CO)(Cl)(NO)(PPh 3 )2r ' bent M-N-O bond.
(iii) In [Cr(CN)s(NO)]3-, presence of the 1t-acid CN- ligands at the electron-poor early transition
metal centre favours the presence of NO+, i.e. the complex is [CrI (CN)5(NO+)]3-. The present
example is very much comparable to the nitroprusside ion.
ry
(E) [Fe(NO)4]' i.e. iron tetranitrosyl: It is isolated as black solids when [Fe(CO)5] is heated with NO
at 45°C. The v NO stretching frequencies are: 1810 em-I, 1730 cm- I, and 1140 cm- I. It supports the
ra
presence of both NO+ and NO-. [Fe(NO)4] has been formulated as [Fe(NO+)3(NO-)] (total valence
ib
electron count = 8 + 3 x 3 + 1 x 1 = 18).
yl
9.7 CYANIDO COMPLEXES
m
9.7.1 Characteristic Properties of CN- as a Ligand
(i) Isoelectronic with CO and comparison with CO: CN- is isoelectronic with CO. So, apparently
he
its ligating behavour is similar to that of the 1t-acid ligand CO. But its a-donor property and 1t-
acceptor property are of different magnitudes compared to those of CO.
a-donor strength: CN- ) RNC ) NO+ -- CO
1t-acceptor strength: CN- <N 2 <CNR < CO <NO+
lc
ea
Compared to CO, the higher a-donor property and weaker 1t-acceptor property of CN- arise
because of the two reasons.
th
• Higher negative charge on CN- makes it a better a-donor and a weaker n-acceptor.
e/
• Less electronegativity of N (compared to that of 0) makes CN- a better a-donor and a weaker
n-acceptor.
t.m
CO can stabilise the lower oxidation states but depending on the condition, CN- can stabilise both
the low and high oxidation states and this will be explained later. To stabilise the higher oxidation
states, the relatively better a-donor property and weaker n-acceptor property of CN- are of
importance. Besides these, the entropic favour arising from the charge neutralisation also operates.
e
Hydrogenase enzyme contains both the CO and CN- ligands bound to iron. The mixed ligand
er
complexes like [Fe(CN)5(CO)]3-, [Fe(CN)4(CO)2]2-, [Fe(CN)3(CO)3]- are relevent to the

hydrogenase enzyme.
H
(ii) Strong field ligand character: It arises mainly due to its n-acidic property. It favours the forma-
tion of low spin complexes.
k
(iii) High nephelauxetic effect: The metal to vacant n*-MO of CN- back bonding leads to the
lic
delocalisation of metal-electron cloud giving rise to a good nephelauxetic effect. This good
nephelauxetic effect reduces the electron pairing energy (P) to favour the formation of low spin
C
complex.
This both strong field character and nepheiauxetic effect are jointly responsible for favouring the
low-spin complex formation.
(iv) Ambidentate character: Depending on the condition, CN- can bind either through the C-end
(softer end) or N-end (harder end). The C-bonded CN- is a strong field ligand while the
N-bonded CN- is a weak field ligand.
(v) Stabilisation of both low and high oxidation states: CO is well known to stabilise the low
oxidation state but depending on the condition, CN- can stabilise both the low and high oxidation
state. Obviously, the low oxidation state stabilisation occurs from the n-acidic character of CN-
while the higher oxidation state stabilisation occurs from the good a-basic character of CN-. CO
is a very poor a-basic ligand and consequently it fails to stabilise the higher oxidation states.
• Mechanism of stabilisation of low oxidation state by CN-: It has been already mentioned that
CN- is a very poor n-acceptor ligand with respect to CO. In fact, the n-acceptor property of CN-
is well expressed only in the complexes having the very low oxidation states like Nio, Ni+, Mn+
etc. In such cases, a-basicity and 1t-acidity may operate synergistically, at least to some extent.
ry
• Mechanism of stabilisation of higher oxidation state by CN-: This is attained mainly due to the
good a-donor property ofCN-. Obviously, in such complexes, the n-back bonding is less important.
ra
The charge neutralisation causes an enormous amount of entropic benefit in solution. The charge
neutralisation removes the electrorestriction over the solvent molecules to introduce this entropic
ib
benefit. Both the good a-basicity and entropic favour are the driving forces to stabilise the
yl
higher oxidation states.
CO is a very poor a-basic ligand. Being neutral, it cannot bring about the entropic favour in
m
complexation with the higher oxidation states. This is why, CO fails to stabilise the higher oxida-
tion states. In fact, because of the very good n-acceptor property of CO, it can only stabilise the
he
low oxidation states.
Examples of stabilisation of low oxidation states: K 3[Ni l (CN)4], K4[Nio(CN)4], K 3[Cu l (CN)4],
K[Au 1(CN)2]' [Mn l (CN)6]5-, etc. lc
Examples of stabilisation of high oxidation states: K3[Mn III (CN)6], K3[CO IlI (CN)6], [Mo Y(CN)8]3-
ea
etc.
th
Ni-cyanido Complexes: [Ni(CN)4]X (x = 2 -, i.e. Ni Il ),

x = 3 -, i.e. Nil.
e/
x = 4 -, i.e. Nio),
Mn-cyanido Complexes: [Mn(CN)6r: (x = 3 -, i.e. Mn IlI ,
t.m
x = 5 -, i.e. Mn l )
Mo-cyanido Complexes: [Mo(CN)8]X (x = 3 -, i.e. Mo Y ,
x = 4 -, i.e. MOlY,
e
x = 5 -, i.e. MO IIl ).
er
The above examples indicate that even for a particular metal centre, CN- can form the
stable complexes with different oxidation states.
H
Note: The cyanido complexes are readily formed by treating the metal ions with the CN-ligands.
k
But the cyanido complexes of lower-valent metal ions cannot be prepared in this route. These are
lic
generally prepared by reducing the higher-valent cyanido complexes in liquid NH 3 by using the
reducing agents like alkali metals. They can also be reduced electrolytically. It is illustrated below.
C
Such complexes of low-oxidation states are generally stable in absence of air and water.
(vi) Different m~des of coordination of CN-: This aspect is discussed below in a separate section.
(vii) Shifting of VCN upon coordination (see Sec. 12.1.17): In most of the cyanido complexes, VeN
increases compared to that of free CN- (cf. for the carbonyl complexes, the reverse is true). In
fact, in the complexes of CN-, the ligand ~ metal a-donation is more important than the
ligand +-- metal 1t-acceptance because CN- is a better a-donor ligand but a weaker 1t-acid
ligand. The a-donation occurs from an orbital which is weakly antibonding in character (cf.
Fig. 9.4.9.1 and the discussion given in connection with CO as a ligand). Thus this a-donation
from the CN-ligand enhances the veN stretching frequency. Moreover, a-donation from the
C-end which is less electronegative than the N-end, strengthens the C-N bond. In general,
for the ligand LXm if L is the donor site then the following situations will arise (see Sec. 12.1.16):
• When XL ) Xx (i.e. donor site L is more electronegative than X as in NH3 ):
ry
(p\-) (q\+) (P2-)
Xn_1L - X, XnL ~ M, PI) P2' i.e. ionic character in the L-X bond decreases upon coordi-
ra
nation. It makes the L-X bond to elongate upon coordination. It makes the L-X bond weaker
(Lf effect of covalent-ionic resonance) (ef VN-H: NH 3 (free) )M f - NH 3).
ib
• When XL ( Xx (i.e. donor site L is less electronegative as in binding through the C-end CN-):
yl
(P 3+) (qr) (P 4 +)
X L- X X L ----? M P4) P3' i.e. more ionic character is introduced in the L-X bond
m
n-I 'n '
after coordination.
he
Considering the effect of a-donation from the weakly antibonding orbital (cf. Fig. 9.4.9.1) and
Xc ( Xlv, we can explain the shifting of v CN- towards the higher values upon complexation.
lc
ea
Complex: [Ni(CN)4]2- [Pd(CN)4]2- [Pt(CN)4]2-} -208{) -I
v eN - 'J em
v CN (cm -I ) : 2128 2143 2150 (in free CN-)
th
Increasing trend of a -donation by CN- and

electronegativity order: Pt II > Pd II > Ni II
e/
[ ylI(CN)6r-
t.m
Complex: [ yIIl(CN)6r-
V
CN
(cm- I ): 2065 2077
Increasing trend of a-donation by CN- and

e
electronegativity order of the metal centre: yIII)yII) yI .

er
9.7.2 Coordination Modes of CN-

H
(i) Unidentate Character: Generally it binds as a unidentate ligand through the C-end.
k
.-:1 " -
lic
M-C==N ....,..-----1.... M = C = N
Both the a-basicity and 1t-acidity can operate.

C
(ii) Ambidentate character: Sometimes, CN- can bind through its harder N-end, i.e. M-NC. How-
ever, the C-bonded CN- is a strong field ligand because in this mode of binding, it can act as a 1t-
acid ligand (because the vacant 1t*-MO used for 1t-acceptance is mainly concentrated on the C-
end; cf CO for coordination, O-end vs. C-end).
(iii) Bridging ligand property: It can act as a bridging ligand, i.e. M-C ==
N-M'. This is well
illustrated in different polymeric compounds like prussian blue, and many other cyanido-bridged
polymeric complexes. These are discussed in Sec. 1.12. That the coordinated M-C N: group ==
can donate the nitrogen lone pair to H+ or other suitable Lewis acid like BF3 is evidenced by its
Lewis basicity.
K 2[Ni(CN)4] + 4BF3 ~ K 2[Ni(CN ~ BF3)4]

K4 [Fe(CN)6] + 6BF3 ~ K4[Fe(CN ~ BF3)6]
M-C_N: + H+ ~ M-C==NH+
In some rare cases, the 1t-electron cloud of the M-C == N moiety can be used for the bridging
activity.
M-C N
ry
!
ra
i.e.
M'
ib
The bridging property of coordinated CN- is quite important in mediating the electron transfer
reaction through the inner-sphere electron transfer mechanism. This aspect has been discussed in
yl
Chapter 6.
(iv) Tridentate bridging function: It has been noted in CuCN · N03 where each Cu-centre maintains
m
the 5 coordination number: IN (by NH 3 ), 2C (by CN-), IN (by CN-), lCu (by Cu····· ·Cu
he
interaction).
I N
I
N
c~
lc I
ea
-N-C
/:"'" C-N-Cu--------
/ C "Cu-N-
I
"': U/ ~C/
i
th
N N
I
e/
I c~
t.m
/c"
-N-Cu-------- Cu-N-C
/:"'" C - I
~c/ "': U/
I i
e
(CuCN . NH 3)n (Coordination by NH 3 not shown).

er
(v) Change of the EO-value due to complexation by CN-: Depending on the condition, CN- may
stabilise the oxidant or reductant more. It is reflected in the EO-value of the redox couples (shown
H
in Table 9.7.2.1)
Table 9.7.2.1 Effect of complexation by CN- on the EO-values (stabilisation by the CN-ligand and entropic
k
effect on complexation, see Chapter 4)

lic
Couple Eo (V) Stability sequence

C
[Co( 0 H2)6] 3+I[ Co( 0 H2)6] 2+

[CO(CN)6]3-/[Co(CN)6]4- } +1.84
-0.83
Co(II) ) Co(lII)
Co(III) ) Co(ll)
[Fe(OH 2)6]3+I[Fe(OH 2 )6]2+ +0.76 Fe(III) ) Fe(II) Explain
[Fe(CN)6] 3-I[Fe( CN)6]4-
[Fe(bpYh]3+/[Fe(bpYhf+ } +0.36
+0.96
Fe(III) ) Fe(II)
Fe(II) ) Fe(lII)
(Hints: Crystal field effect,
stabilisation of oxidation states
[Cu(aq)]2+j[Cu(aq)]+ +0.15 Cu(II) ) Cu(l) and endtropic effect; see Sees.
[Cu(aq)]2+j[Cu(CN)4P- } »0.15 Cu(I) ) Cu(II) 4.8; 3.14.15
(vi) Reactivity of coordinated cyanide ligand: This aspect has been discussed in Sec. 10.12.
9.8 ISOCYANIDE OR ISONITRILE COMPLEXES

Alkyl or aryl cyanides, i.e. R-C ==
N or Ar-C ==
N are called nitriles (e.g. CH 3CN called ac-
etonitrile or methyl cyanide, cf IUPAC nomenclature) while RNC, ArNC arc called isocyanides or
isonitriles.
+ ..
R-N==C:(I)~R- N =C:(II)
ry
(sp) (sp2)
ra
v eN ::::: 2150 cm- indicates the major contribution of the resonating structure (I) to explain the properties
ofRNC.
== ==
ib
(a) Coordinating property of isocyanides: Isocyanides, RN C: are isoelectronic with :C 0:
Isocyanides can coordinate through the C-end. Like the CO, they can show both the a-donor and
yl
n-acceptor properties. Like the cyanides, the isocyanides are the better a-donor ligands but poorer
n-acceptor ligands compared to co. It happens so mainly due to the lower electronegativity of
m
N compared to that of 0 in CO.
he
a-donor strength: CN- ) RNC ) CO ) NO+; a-donor MO: NBMO with some antibonding
character
lc
7t-acceptor strength: NO+ ) CO » RNC ) CN-; 7t-acceptor MO: Strongly ABMO (i.e. n*-MO)
ea
The electron pair used for a-donation is slightly antibonding in character (ef CO and Fig. 9.4.9.1).
th
This is why, this a-donation enhances the stretching frequency of the C-N bond. The weak 7t-acceptance
occurs in the n*-MO. Thus the n acceptance lowers the stretching frequency.
e/
The coordinating property is greatly influenced by the nature of R. The aryl isocyanides are the
better 7t-acceptor ligands (because of their benzene ring with the vacant 7t*-MOs) than the alkyl
t.m
isocyanides. The higher electronegativity of the sp2- ary l-C, compared to that of the sp3- alkyl-C is also
a reason. This is why, for the low-valent metal centre where the metal ~ ligand n-donation is favoured,
VC- N decreases sharply in the aryl isocyanides.
e
• Aryl isocyanides (ArNC): Weak a-donation but strong n-acceptance in the n*-MO for the metal
complexes of specially low oxidation states (e.g. [Ni(CNAr)4])'
er
VCN: ArNe) [Ni(CNAr)4]' [Cr(CNAr)6]' i.e. VCN is lowered.

H
• Alkyl isocyanides (RNC): Only a-donation and practically no n-acceptance in the complexes,
i.e. VCN is raised in such complexes.
k
(b) Stabilisation of both the low and high oxidation states of the metal centre: Like the cyanides,
lic
the isocyanides can also stabilise the higher oxidation states of metals because of the good a-donor
properties of isocyanides. The examples are: [V(CNR)6]+, [Cr(CNR)6]3+, [Pt(CNR)4] 2+, etc. In such
C
cases, the n-back bonding (metal ~ ligand) is of no significance. Thus the M-CNR a-bond can
independently stabilise the complex without the n-bonding (ef stability of the carbonyl complexes
largely depends on the synergistic n-bonding). However, for the low oxidation states, the synergistic
n-bonding as in the M-CO linkage is the important factor to stabilise the M-CNR linkage. In fact,
several homoleptic uncharged metal isocyanides corresponding to the metal carbonyls have been
prepared. Some examples are:
Carbonyl Complexes: [Ni(CO)4] [C0 2(CO)g] [MO(CO)6]
Isocyanide Complexes: [Ni(CNR)4] [C0 2(CNR)8} [Mo(CNR)6]
[Ni(CO)4] + 4RNC ~ [Ni(CNR)4] + 4CO.
(c) Comparison with CO: It has been already mentioned that RN ==

C is a better a-donor ligand
than C == 0 but it is a poorer n-acceptor ligand than CO. This is why, the M-CNR a-linkages are self
sufficient to stabilise the relatively higher oxidation states like Cr(III), Mn(II), Fe(II), Fe(III), etc. In
such cases, the n-bonding (i.e. n-acidic character of RNC) is of no significance. But carbonyl fails to
form any stable' complex with these metal ions because stability of the M - CO linkage largely de-
pends on the n-back bonding (i.e. metal ~ CO). In the case of such high positive oxidation states, the
ry
metal ~ ligand n-back bonding is not efficient. The selective preference of CO for the lower oxidation
state of metal is evidenced in the following reaction, i.e. disproportionation of [C0 2 (CO)s].
ra
[Co 2(CO)s] + 5RNC ~ [Co+ 1(CNR)s][Co- 1(CO)4] + 4CO.
ib
Here RNC goes to + 1 oxidation state while CO goes to -1 oxidation state. It may be mentioned that
in the cation [Co(CNR)s]+ , there is also n-back bonding to some extent. It is supported by the fact that
yl
the Co-C bond length (-185 pm) is shorter than the single Co-C bond length (207 pm). However,
the n-back bonding is more important in the anion, [CO(CO)4]-.
m
(d) Lin!ar or bent C - N - C segment in the terminal M-CNR groups: In most of the cases,
he
the C -;:- N - C angle is almost linear (ca. 165 - 180°) while in some cases the segment is angular (i. e.
C- N- C ~ 130 -135°). By considering the valence bond models, the structures of the
M-CNR linkage may be shown as follows. lc
ea
1t-donolQ
property.. Sp2- N
N'/
th
E
R-N==C: Weakly antibonding
character to this
{?/c
~ ""'R
e/
lone pair
Mil'
(ct. R-C==N: (nitrile)
t.m
C-N-C segment
C-N-C segment
Dipole moment: nitrile < isonitrile (almost Ii near)
(angular) (lone pair residing on M,
(lone pair residing on N, suitable for 1t-back bonding)
suitable for 1t-donation)
e
cf. linear and bent M-N-O linkage in the nitrosyl complexes (Sec. 9.6.2)
er
H
k
1t-acceptance
lic
It is evident that in the angular C-N-C segment, the ir-stretching frequency (VNC) is relatively
less compared to that in the linear linkage (see Sec. 12.1.17).
C
[Ru(CNBu t)4(PPh 3)]: V NC (linear) ) VNC (bent)·

The metal-carbon 7t-bonding (i.e. double bonded character in the M-C bond) occurs for the
angular C-N-C segment. In a trigonal bipyramidal geometry, the said metal-carbon n-bonding can
occur efficiently when the isocyanide group remains bound at the equatorial position. This is evidenced
in [Ru(CNBut )4(PPh 3)] (trigonal bipyramidal geometry) where the two t-BuNC groups (along with the
PPh 3 group) at the equatorial positions are bent to allow the metal-carbon n-bonding. But the t-BuNC
groups present at the axial position are almost linear because, the axial groups of a trigonal bipyramidal
geometry cannot participate in n-bonding. Similarly, in [Fe(CNBut)s], the equatorial t-BuNC groups are
bent.
N
R/ " . IN
c------------- cDR Bent
} Linkage
/BU' \~ / ; ' 137'
ry
(Fe===c === ~ ~ 137°); R - - N C - -.....
'.---Fe " C N-R
(equatorial position)
\"" 11,,"/ '-y----J
ra
Linear linkage
(Fe===C===N--Bu ~ 180
t \ I
0
ib
(axial position)
II
yl
:N~
R
m
Depending on the condition, the isonitrile group can act as a a-donor, as a 1t-donor and as a
he
1t-acceptor. For the alkyl isonitriles, the n-acceptance property is negligible but for the aryl isonitriles,
the n-acceptor ability (to reduce the v eN value) is quite good and almost comparable to that of CO.
Here it is worth mentioning that the electron pair used for a-donation is having some antibonding
lc
character. Thus when, isonitrile acts basically as a a-donor ligand (specially for the positive oxida-
ea
tion states of the metal centre) (i. e. for the linear M-CNR linkage), the stretching frequency is
slightly increased in the complex compared to that of free RNC.
• Alkyl isocyanides (RNC): VC-N = 2140 cm- l (in free RNC) (VC- = 2245 cm- l in [Ni(CNR)4]2+
th
N
R = l-C 4 Hg
e/
The same thing occurs when CO binds mainly through the a-bonding as in the non-classical carbo-
nyl complexes, e.g. [Ag(CO)]+, [Au(CO)]+ where n-back bonding is insignificant.
t.m
The linear linkage M-CNR (i.e. a-only bonding) is predominantly found under the conditions:
(i) relatively higher positive oxidation state of the metal centre:
(ii) R = alkyl group (cf. for R = Ar, the n-acceptor ability of isocyanides is enhanced because of the
e
presence of vacant n*-MOs of the benzene ring system and higher electronegativity of aryl-C).
er
For the aryl isocyanide complexes of low valent metals (e.g. Nio, Cro, etc.), the n-back bonding is
very much important and VCN is lowered as in the case of classical carbonyl complexes.
H
• Aryl isocyanides (ArNC): VC-N (free ArNC) > VC-f' in [Ni(CNAr)4]' [Cr(CNAr)6]
(e) Reactivity of the coordinated isocyanides (cf. Chapter 10): The nucleophilic attack on the
k
coordinated isocyanides can be explained as follows:

lic
.-.
M-C_N-R
0+
C
"--
Nu-
Obviously, the said nucleophilic attack is facilitated for the linear M-CNR mode of coordination,
i.e. where metal-carbon n-bond is relatively inefficient. By, using this technique, Fischer-type carbene
complex can be prepared. This aspect has been discussed in Chapter 10.
9.9 SULFUR DIOXIDE (:S02) AS A 1t-ACID LIGAND ·

Depending on the mode of coordination, the lone pair on the S-centre can be used for a-donation
(planar 111-S02) and the vacant n*-MO can be used for n-acceptance (cf. Fig. 9.5.1). Sometimes, the
n-bonding electron cloud of the 'S-O' linkage may be used for a-donation and the vacant n*-MO may
°
be used for n-acceptance (side-on Tl2-S02)' In this mode, though both the Sand centres coordinate
but they occupy one coordination site as by C 2H4 in Ziese's salt anion, [Pt(C 2H4 )CI 3]-.
The details of coordinating behaviour of S02 have been discussed in Sec. 9.5 and in Fig. 9.5.1.
Coordination by CO 2
ry
CO is a potentialn-acid ligand but CO 2 has been found rarely to act as a ligand. However, CO 2 can
coordinate in some cases. The coordinating style of CO 2 may be compared with those of 50 2 and
ra
CS 2 •
ib
[Rh(C02)2C1(diars)]: CO 2 coordinates through the C-end; Rh lies in the plane of CO 2 having
yl
O-C-O bond angle about 126°.
trans-[Mo(C02)2(PMe3)4]: CO 2 coordinates through the C and °end; Mo lies in the plane of the
m
coordinated CO 2 having the 0 - C - ° bond angle about 130°.
he
lc
ea
Electrochemistry of the coordinated CO 2 is quite interesting. Coordinated CO 2 can be electro-
th
catalytically reduced to formate or methanol in some cases.

e/
Coordination by CS 2
t.m
Compared to CO 2, CS 2 is more active as a ligand.

e
er
H
The common coordinating modes of CS 2 as a ligand are as follows:

k
lic
S-M
/
M-C,\-
C
9.10 PHOSPHINES AND PHOSPHITES AS THE 1t-ACID LIGANDS

(A) Coordinating behaviour of the P(III) ligands: The phosphines are :PR3, :PAr3, :PH3; phosphites
are :P(OR)3, :P(OAr)3; trihalides are :PF3, :PCI 3 etc.
Pi-acidity order of the P(III) ligands: In gene~al, PX 3 can act as the n-acid ligands by using the
vacant 3d-orbital. Thus, in this context, P(III)-ligands are comparable to CO that uses the n* -MO for
n-acceptance.
ry
(d 7t - interaction)
ra
(d 7t - d7t interaction) 11:*
(a) (b)
ib
Fig. 9.10.1 Pi-acceptance by PR3 (a) and CO (b) in their respective metal complexes.
Note: For the sake of ·simplicity, the 3d orbital of phosphorus has been considered to participate in
yl
n-acceptance, but in reality, the vacant antibonding MO participates in n-bonding. For example, in
m
PF3, the P-F antibonding a*-MO mainly constituted by the 3p-orbital of P participates in n-accept-
ance. In the said a*-MO, participation of the 3d orbital is of only minor importace. Similarly, the
he
antibonding P-C or P-O orbitals may participate in the said n-acceptance. The pi-acidity order of
the P(III) ligands is:
lc
CO :::: PF3 ) PCl 3 :::: P(OAr)3 ) P(OR)3 ) PAr3 ) PR3
Thus PH 3 and PR3 (i.e. alkylphosphines) are the weak n-acid ligands but they are quite good a-bases.
ea
In terms of the n-acceptor property, PF3 is quite similar to CO and like CO, PF3 can directly react with
Ni to produce [Ni(PF3)4].
th
(Note: PF3 is a good n-acid ligand and it can stabilise [Ni(PF3)4] but NF3 cannot act as a n-acid ligand
because of the absence of any suitable vacant orbital to participate in the n-back bonding).
e/
CO vs.PF3 and PR3 : In terms of the n-bonding efficiency, PF3 is comparable to CO and in fact, in
many cases, CO group can be replaced by PF3 as in [Ni(CO)4]. But in terms of polarisability, i.e.
t.m
softness, CO is softer than PF3. In fact, this hardness in PF3 is introduced due to the presence of
nonpolarisable, electronegative and hard F-atoms. This is why, in some cases, PF3 fails to produce the
analogues of carbonyls. In fact, [Pd(PF3)4], [Pt(PF3)4] do not exist because the zero-valent Pd and Pt
e
centres are highly soft and they do not combine with PF3. However, PF3 can combine with Ni(O) which
is relatively harder, i.e. hardness follows the sequence, Ni(O) ) Pd(O) ) Pt(O).
er
Here it may be mentioned that though [Pd(PF 3)4] and [Pt(PF3)4] do not exist but [Pd(PR 3)4], [Pt(PR3)4]
(R = Me, Et) exist. It is due to the fact that PR3 is softer than PF3.
H
(B) Factors cotrolling the n-acid strength of the P(III) ligands: The following factors are important.
(i) Electronegativity of the substituents: For the more electronegative substituents, the more electron
k
deficiency is generated at P(III) and it makes the ligand a better n-acceptor one. It explains the n-
lic
acid strength order:

PF3 ) PCI 3; P(OR)3 ) PR3; P(OAr)3 ) PAr3.
C
(ef OR is more electron withdrawing than R; similarly, the OAr group is more electron withdraw-
ing than the Ar group)
(ii) Aromatic phosphines vs. aliphatic phosphines: The aromatic phosphines are the better n-accep-
tor ligands, i.e. PAr3 ) PR3. It is because of the presence of the vacant n*-MOs of the benzene
ring system and the higher electronegativity of the aryl-C.
(C) Steric factor measured by Tolman's cone angle (8): When the ligands are bulky, the ligand-ligand
stenc repulsion is relieved by elongating the metal-ligand distance. Consequently, it will weaken the
metal-ligand bonding interaction. The steric requirement of a ligand is measured by the volume of
space occupied by the ligand. For the PX3 ligands, this stenc requirement cannot be exactly estimated
by the X - P-
X bond angle but may be estimated from the molecular modelling or construction of
the space-filling model. Tolman, expressed this steric requirement in terms of cone angle (8) which is
the apex angle of a right cylindrical cone. This apex angle is produced at a distance of 228 pm away
from the P(III) centre by the tangents to the van der Waal's radii of the X-groups (Fig. 9.10.1). The
reference distance 228 pm between the centre of the metal centre and tip of the cone is taken on the
basis of Ni-P bond distance. Cone angles for some representative P(III) ligands are given in Table
ry
9.10.1.
ra
Table 9.10.1 Cone angles (8) for some representative P(III) ligands.
ib
Ligand (J (degree) Ligand (J (degree)
yl
PMe3 118 . P(OMeh 107
PEt3 132 P(OEt)3 109
m
PBU3 132
he
PEtPh 2 140 PMe(OEth 112
PPPh 3 145 P(OPh)3 128
P(i-Prh 160 P(O-i-Pr)3 130
PCY3 170
lc P(OEt)Ph 2 133
ea
P(t-BU)3 182 P(OCyh 141
PC1 3 124
th
Cy = cyclohexyl
e/
It has been noted that cone angles greater than 140 0 produce a significant stenc crowding. When all
other factors are comparable, the small cone angles ensure the better metal-ligand interaction by
t.m
allowing the closer approach of the ligand towards the metal centre.
e
er
pmr_-_- ~ -_] 228 pm

H
-228
k
lic
Fig. 9.10.2 Tolman cone angle (8) for PR 3 in M-PR 3"
Cone angle for other ligands: The idea of cone angle (8) measuring the volume of space occupied
C
by a ligand in the coordination sphere can also be extended for other ligands by considering the space-
filling model. Tolman cone angle (8) for some other ligands are given in Table 9.10.2.
Table 9.10.2 Tolman cone angles (8) for some representative monodentate ligands
Ligand: H Me F CO CI Et Br Ph I t-Bu
e (degree): 75 90 92 95 102 102 105 105 107 126
The ligands like CO, PF3 etc. having small cone angles are described as the slim ligands while the
ligands like PPh 3 , P(i-Pr)3 etc. having large cone angles are described as the fat ligands.
(D) Flouting the 18e-rule for the large cone angles: When the stenc requirements are of no significance
as in the case of slim ligands like CO, the ligands may be added as required by the 18e rule. But, for
the bulky ligands (i.e large cone angle), it may not be possible to satisfy the 18e rule by adding the
required number of ligands because of steric crowding. It is illustrated in the following examples.
(i) Dissociation constant (K n ) for [Ni(PR3)4}:::~[Ni(PR3)3J+PR3and[Ni(PR3)4J~
ry
[ Ni (PR 3 )2] + 2PR 3: In terms of the 18e rule, [Ni(PR3)4] (18e configuration) should be stable but the
dissociated products, i. e. [Ni(PR3)3] (16e configuration), [Ni(PR 3 )2] (14e configuration) should be
ra
relatively less stable. Thus the dissociation equilibrium should lie towards the left. It has been noted that
ib
for the small PR3 ligands (8 ( 130 - 135°) the dissociation constant is exceedingly small as expected
from the 18e rule, but for the bulky PR3 ligands (8 ) 145°), the dissociation constant is very high.
yl
Thus, the dissociation constant gradually increase with the increase of the cone angle of PR 3. It has
been noted that [Ni(PBuj)4] dissociates to such an extent that the 14e-product [Ni(PBuj)2] can be
m
isolated, i. e.
he
[ Ni(PBu~)4J ~ [Ni(PBu~)J+ 2PBu~
(ii) [Pt(PMe3)4], [Pt(PEt3)4] vs. [Pt(PBtlj )2]: The cone angles for PMe 3, PEt3 and pet - BU)3 are 118,
lc
132 and 182, i.e. steric requirements follow the sequence: pet - BU)3 » PEt3 ) PMe3. Thus the 18e
ea
configuration can be maintained for the smaller ligands as in [Pt(PEt3)4] or [Pt(PMe3)4]. But, it is not
possible for the bulky ligand pet - BU)3 and the stable product [Pt(PBu3()2] attains the 14e configuration.
th
In fact, the 18e-product [Pt(PBu3()4] dissociates to the 14e product to avoid the steric crowding, i.e.
[Pt(PBu~tJ ~ [Pt(PBu~)J + 2PBu~

e/
(Note: [Pt(PR3)4] (R = Me, Et) exists but [Pt(PF3)4] does not exist. This observation can be explained
t.m
in terms of hard-soft character matching not in terms of stenc crowding. This aspect has been already
discussed).
e
er
H
(iii)
k
lic
In the prduct, the electronic factors favour the cis-product, i.e. cis-[W(CO)4(PX 3)2]. The, n-bonding
C
efficiency rings as: CO ) PX 3. This is why, CO prefers the weak competing PX3 ligands at the trans-
position (cf Fig. 9.4.11.5). This requirement is satisfied in cis-[W(CO)4(PX 3)2]. For the less bulky
PX3 ligands (i.e. cone angle ( 130°), the cis- product predominates according to the electronic demand
of the CO group. But for the bulky PX3 ligand (cone angle) 130° - 135°), the trans-product predominates
because in trans-[W(CO)4(PX 3)2], placement of two bulky PX3 ligands at the trans-positions leads to
a less stenc crowding.
Thus in [W(CO)4(PX 3)2], for the less bulky PX3 ligands, the electronic demand of CO determines
the configuration while for the bulky PX3 ligands, the steric factor determines the configuration. It has
been noted for 8 ) 130°, the % of trans-product increases with the increase of 8.
(iv) [MO(CO)6] vs. [MO(CO)3(PPr~)2]: In [MO(CO)6]' the 18e rule is satisfied but in [MO(CO)3(PPr~)2]
which is obtained by the replacement of three CO groups of [MO(CO)6] by two P(i -Pr)3 groups, the 16e
configuration is attained because the steric crowding in it does not allow the accommodation of another
ligand to attain the 18e configuration. However, the small ligand like H2 can coordinate to give the 18e
product. Thus Kubas (in 1983) prepared the dihydrogen complex.
ry
[MO(CO)6] 2P_~~~)3 >[ MO(CO)3 (pprn 2],(16e product)
(18e)
ra
1 H2
ib
yl
[MO(CO)3(1l2-H2)(PPrnJ, (18eproduct)
m
The available space in the coordination sphere of [MO(CO)3(PPr~)2]can accommodate the very small
ligands to attain the 18e configuration. In fact, H 2 may be added to [MO(CO)3(PPr3i)2] to give the 18e-
he
product. Thus the steric factor controls the product.
In the same way, the following dihydrogen adduct was first prepared by Kubas (1980).
[M(CO)3(PCY3)2] (16e) + H 2 ~ [M(CO)3(1l2-H 2)(PCY3)2] (18e) (M = Mo, W; Cy = cyclohexyl)
lc
In such dihydrogen adducts, H 2 remains as 112-H2.
ea
(v) Degree of photochemical substitution of CO in [MO(CO)6] by PR3:
[MO(CO)6]+PR 3 ~;~ ) [M(CO)s (PR 3)]+CO.

th
The above photochemical substitution reaction goes on but the extent of substitution depends on the
e/
cone angle of PR3. For the less bulky PR3 ligands like PMe3 (8 = 118°), PEt3 (8 = 132°), the product
[MO(CO)3(PR3)3] (i.e. substitution of 3CO groups in [MO(CO)6] by 3PR3 groups to maintain the 18e
t.m
configuration) is obtained. But, for the bulky ligands like, P(i-Pr)3 (8 = 160°), P(t-Bu)3 (8 = 182°), it
will not possible to have the product like [MO(CO)3(PR3)3] (18e) because of the steric crowding. Rather
to compromise with the steric factor, the 16e product like [MO(CO)3(PR3)2] becomes stable for the such
e
bulky PR3 ligands. It may be mentioned that substitution of CO by PR 3 favours the pi-back bonding
with the remaining CO groups (ef 9.4.11.5).
er
9.11 CHEMISTRY OF DINITROGEN COMPLEXES: ACTIVATION OF DINITROGEN

H
These aspects have been discussed in Sec. 1.7 and 10.12.10 in detail. Here we shall discuss the
coordinating style of N 2.
k
(a) Very Poor Coordinating Power of N2 Compared to its Isoelectronic Species CO, NO+ etc.: N2
lic
is chemically inert and it is also a very weak ligand. It is isoelectronic with CO. There is a large number
of complexes where CO acts as a ligand but there are only few complexes in which N2 acts as a ligand.
C
In fact, the accidental discovery of [Ru(NH 3)s(N 2)]2+ by Allen and Senoff (in 1965) is the first recorded
dinitrogen complex (a case of scientific serendipity; ef Sec. 9.1.3). [Ru(NH 3)s(N 2)]2+ can be prepared
in the reaction of [Ru(NH 3)s(OH 2)]3+ with azide ion (N 3-). Here Ru(III) is reduced to Ru(II). N 2, CO
and NO+ are the isoelectronic species but N2 is the least promising one as a ligand among these three
isoelectronic species. In fact, numerous complexes of CO and NO+ are well known.
The poor ligating property of N2(compared to that of CO and NO+) can be rationalised by considering
its MO energy diagram. N2is a homonuclear diatomic spacies while CO and NO+ are the heteronuclear
diatomic species where the atomic orbitals of the two atoms available for the constructions of the MOs
are of different energy.
II ,
1/ \\
I I \\
"/, " " 21t;

\
~" \ \
I / LUMO \ \ \
I / I \ \ \
I I I ~ \
I / I ~ \
ry
I / I \\ \
~:/ \\~~
1;// I \ ""
,/
ra
~~~, ,/ HOMO ~/~~ +
ib
\\\ ,I ) ; ' \/1
\ \ \ ", Sag
\\\ ' 1
'11\ , '1-L" ;'
;';' / (/ 1
/ /101
I \1
t
yl
\ 1\ \ I \ / I
\1 \ \ I \ / I 1
\{'\~/.c. I~
,'" ,,\
4
~(
I
/
m
\
I ~ \ 11t1 \ 1 \
I 1\ \ jU '" \
11\ \~ 1\\
',I \ \
he
I I \,,"
II ,,'( 4 * .,.. \ \ LUMO of N2
~
/"" \ au I', \ \ ~
"\ 1 ',~
25 ',,, / // 25
'" ,
" \
/
1 /
///
lc
3ag "~~/
ea
th
HOMO of N2
e/
t.m
Fig. 9.11.1 Molecular orbital diagram of dinitrogen (N 2) (see Vol. 2 for details).
e
(b) Nature of HOMO for a-donation in N2: In CO and NO+, the HOMO is basically a nonbonding
er
MO primarily concentrated on the less electronegative centre (i.e. C-end in CO and N-end in NO+).
This NBMO (i.e. HOMO) is mainly constituted by the 2p-orbitals of the less electronegative atom. This
H
nonbonding electron pair is suitable for a-donation. On the other hand, in N 2 (cf. Fig. 9.11.1 for MO
energy level diagram of N 2), the HOMO is a a-BMO, i.e. the electron pair is concentrated between the
k
N-atoms for a-bonding. Consequently, this HOMO electron pair is not suitably oriented for a-donation
in the linear TIl-mode of coordination (i.e. ,,2-N2, end-on terminal; Fig. 9.11.2). It is evident that the
lic
deeply seated ~-MO (::::: a;s' a-ABMO) basically constituted by the 2s-orbitals of N-atoms is suitably
oriented for the linear 1l1_N2 coordination but this a-donation is energetically very much unfavourable.
C
Here it is worth mentioning that in the ,,2-mode of coordination (i.e. ,,2-N2, side-on terminal;
Fig. 9.11.2), the HOMO (i.e. a-BMO) is suitably oriented for coordination but this tightly bound
a-bonding electron pair can hardly be donated. All these make N2 a very poor a-donor ligand. In fact,
in terms of its a-donor property, it is the weakest one among the isoelectronic species NO+, CO
and CN-.
(c) Nature of LUMO for 1t-acceptance in N2: In CO and NO+, the LUMO is a n*-MO which is
mainly located on the less electronegative end. In N b the LUMO is also a n* -MO but not concentrated
on any end. Thus, the LUMO of NO+ or CO is more suitable for the n-type overlap with the metal
d-orbital compared to the case of N 2 • It makes CO and NO+ better 1t-acceptors.
(d) Effect of the more electronegative heteroatom in 1t-acceptance: In CO or NO+, presence of the
more electronegative O-atom favours the electron flow towards the ligand from the metal. In N2, there
is no such driving force for the metal to ligand electron flow. It also makes N2 a poorer 1t-acceptor
ligand. It has been found that the n-acceptor property of N2 is comparable to that of nitrite but it is very
much less compared to that of NO+ or CO.
(e) Weak synergistic action: Generally, for the n-acid ligands, the a-donation (i.e. a-basicity) and
ry
n-acceptance (i.e. n-acidity) work synergistically in the metal-ligand bonding interaction. But because
of the unfavourable nature ofHOMO and LUMO and lack of electron withdrawing force in the ligand
ra
for the metal ~ ligand n-acceptance, both the a-donation and n-acceptance are very much weak for N2
as a ligand. Between these two interdependent bonding interactions, the C1-donation is of very poor
ib
magnitude, but the n-acceptance is relatively better. However, this n-acceptance is less significant
yl
compared to the case of NO+ or CO. This is why, N 2 is so reluctant in forming the complexes.
(f) Relative contribution of the 0'- and 1t-bonding in M-N 2 bond: From the independent studies
m
on the dinitrogen complexes, it has been found that N2 acts as a very poor a-donor ligand. Stability of
he
the metal-N 2 bond mainly depends on the 1t-acceptance property of N2 •
(g) Enhanced reactivity of the coordinated N2 : Coordinated N2can act as a better ligand than free
N 2. Coordinated N 2 can act as bridging ligand. These aspects have been discussed in detail in Chapter
10 and in the author's book, Bioinorganic Chemistry.
lc
ea
(h) Some representative dinitrogen complexes:
RuCl 3 (contaminated by Ru IY ) -(-i.e-.r---,~~,--~-~:-~~_eo-f----+)[ Ru(NH 3 )5 (N 2) r+

th
Ru lV by NH NH
2 2)
e/
This was the route of the accidental discovery (a case of serendipity) of the said dinitrogen complex
by Allen and Senoff (1965). Their paper of this accidental discovery of the unprecedented dinitrogen
t.m
complex was first rejected for publication in J. Am. Chem. Soc. but ultimately it was published in
Chem. Commun., 621-22, 1965. This complex can also be prepared as follows:
e
er
Probably the intermediate azido complex, i.e. [Ru(NH 3 )s(N 3)]2+ undergoes the redox decomposi-
H
tion to give the said dinitrogen complex. This can also be prepared in the following route.
r~duction by Zn(Hg) ) [Ru (NH ) (N )J2+
k
(m N 2 atmosphere) 3 5 2
lic
The relatively more electron rich coordinated N2 (n-acceptance in the n*-LUMO) is more reactive
than free N2and it can more readily act as a bridging ligand.
C
[Ru(NH 3 )s(N 2)]2+ + [Ru(NH 3 )s(OH 2)]2+ ~ [(H 3N)sRu-N 2-Ru(NH 3)s]4+ + H20
Absence of other competing 1t-acceptor ligands, presence of good a-donor ligands like NH3,
PR3 and low oxidation state of the metal centre favour the M --+ 1t*(N2) 1t-back bonding to stabililise
the dinitrogen complex. The [M(CO)s(N 2 )] and [M(CO)4(N 2)2] (M = Cr, Mo) complexes are only
marginally stable but the complexes like [M(CO)3(N 2)(PR 3)2] are relatively more stable. It is due to the
fact that PR3 is a much stronger a-donor ligand but a much weaker n-acceptor ligand the CO. In fact,
PR3 as a good a-donor ligand favours the M ~ N2 n-back bonding.
[MO(CO)3(PCy )J(16e) + N 2 ~[MO(CO)3 (N 2)(PCY3)2 J; Cy = Cyclohexyl

Examples of dinitrogen complexes relavant to N2-fixation are:
[ MoCI3(thf)3J-N_a_-H=--go_rM.......:;g~)
excess dppe, N 2
[Mo(dppe)2 (N 2)2] + 3CI- + 3thf
thf = tetrahydrofuran
dppe = Ph 2PCH 2CH 2PPh 2 1 H+ ~~gN~r Mg,
ry
(good a-donor)
N2 + NH4+ + Mo(VI)-product
ra
ib
yl
m
he
lc
ea
th
l Mea[16]anes4 )
e/
-----~-----
~
t.m
bis(dinitrogen)crownthioether complex,
trans-[Mo(Me a[16]anes 4)(N2)2)]
(115-Cp)2Ti - N==N -Ti(115-Cp)2 (N 2, a bridging ligand)

e
/1""
er
N
Coordinating modes of N2
-CPl2sm~ /sm(T] 5-Cpl
(T] 5* * 2
H
M~N==N M~N==N~M
End-on terminal End-on bridging
1 1 N
Linear ll1-N2 Linear 1l-11 : ll - N2
k
2 2
1 - N2
f.l-11 : 11
Il (bis-ll
lic
)
i. e. side-on bridge
(a) (b)
N
1
III
C
N (11 - N2)
M~III i.e. T]2-N2
N
I 1
1l-11 : ll - N2
s
1
N (l1s-*Cp)2Zr- N==N-Zr(l1 -*Cp)2

Side-on terminal Side-on bridging
2 2 N
I
(c) 1l-11 : 11 N2
2
-
III (Cp = CsMe s)
Il (bis-11 ) N
(d)
Fig. 9.11.2 Coordinating behaviour of N2 in different complexes.

Dinitrogeri complex of Mo(O) in an acidic condition in presence of the strong reducing agent like
Na-Hg or Mg can catalytically carry out the reduction of N 2 to NH 4+(6e transfer, Mo(O) ~ Mo(VI».
The above reaction is important from the standpoint of nitrogen fixation and understanding of the
activity of the nitrogenase enzyme.
The following dinitrogen complexes of Mo(O) and W(O) can also reduce N 2 to NH 4+.
ry
H2S04 + ()
[ M ( N 2 ) 2 ( PPh 2Me ) 4 ] ) N 2 + 2NH 4 + M VI -products.
(CH 30H)
ra
The dinitrogen complexes, [IrCI(N 2)(PPh 3)2], [Co(H)(N2)(PPh 3)3], [Mo(Me 8 [ 16]aneS4)(N2)2],
[(115-Cp)2Ti-N2-Ti(115-Cp)2 ], [{ (11 5- *Cp)2(N2)Zr }2(N2)], [(11 5- *Cp)2Sm(N2)Sm(11 5- *Cp)2] are quite
ib
interesting to the inorganic chemists.
yl
(i) Shifting of VN-N upon complexation (see Sec. 12.1.17): N 2 (in free state) is ir-inactive but Raman
active (V N- N = 2331 cm- I , Raman stretching frequency). The coordinated N 2 is ir-active. Coordinating
m
power of N 2 is mainly determined by its weak 1t-acceptor property, i.e. M ~ n*-MO (N 2). It reduces
he
the N-N bond order, i.e. lowering of VN- N upon complexation. This has been experimentally verified
in many dinitrogen complexes. The stretching frequency VN- N in some dinitrogen complexes are given
below (cf. Sec. 12.1.17):
VN-N (cm- I ): = 2331
lc
(free N2); 2130 in [Ru(NH 3)5(N 2)]2+; 1955 and 1890 in
ea
trans-[Mo(N2)2(Me8[16]aneS4)]; 2095 in [IrCl(N 2)(PPh 3)2]; 2088 in [Co(H)(N 2)(PPh3)3]
th
9.12 CHEMISTRY OF DIHYDROGEN COMPLEXES: ACTIVATION OF DIHYDROGEN

(cf. Sec. 10.12.11)
e/
The following dihydrogen complexes were first prepared by Kubas in 1980-84.

[MO(CO)3(PPr3i)2] (16e) + H 2 ~ [MO(CO)3(PPr3i)2(112-R~H18e); (cf. Sec. 9.10)
t.m
The 16e compound is sterically crowded (cf. cone angle for the PR 3 ligands; Sec. 9.10) and it can
accommodate only the small ligands like H 2. Tungsten (W) can also produce the similar compound.
In the same way, the following dihydrogen complex was prepared.
e
[MO(CO)3 (PCY3)2]C16e) + H 2 ~ [ MO(CO)3 (T\2-H2 )(PCY3)2] (l8e), Cy = Cyclohexyl group.

er
Depending on the condition, M(112-H2) (i.e. dihydrogen complex) may be converted into
H
cis-M(H)2 (i.e. dihydrido complex, through the oxidative addition of H 2). Vaska's complex reacts with
H 2 giving rise to the dihydrido complex.
k
H
lic
PhP~ I ~H
~
C
- - - - - : l. . Ir"
CI/ I ~PPh3
C
o
112-H2 (i.e. side-on terminal) can act as a 1t-acid ligand by donating its electron from the cr-BMO and
accepting electron in its cr*-ABMO, i.e.
cr-BMO(H 2) ~ M and M ~ cr*-ABMO(H 2)
Both these functions will weaken the H-H bond (i.e. decrease OfV H _ H ). In the dihydrogen complexes,
generally it has been found as (see Sec. 12.1.17):
ry
ra
ib
yl
m
he
---. z-axis
lc
ea
, Fig.9.13.1 Coordinating behaviour of O 2 (dioxygen) and simple MO energy diagram of O 2•
To understand the coordinating behaviour of 02' we should consider the MOs of O 2 (Fig. 9.13.1). For
°
th
the highly electronegative elements like and F, the high energy difference between the 2s and 2p
orbitals does not allow their mixing in constructing the MOs (see Chapter 9, Vol. (2). Consequently, the
e/
simple MO diagram can explain the properties of 02. Its electronic configuration is:
KKcri(2s)cr:2(2s)cri(2Pz)n~(2px, 2p.'Jn;2(2px, 2P.'.), z-axis the molecular axis.
t.m
0
o~o
II ~o z
0
0
)-'x
e
M
M
er
M Y
H
k
lic
C
@ Metal ion
o Oxygen atom
2 1
(a) 11 -0 2 (c) 11 -02
Fig. 9.13.2 Different modes of coordination in the M-0 2 complexes. (a) Perpendicular mode (edge-on overlap); (b)
Linear mode (end-on overlap); (c) Bent end-on overlap.
The pn*-MOs are singly occupied (i.e. SOMOs) and these are the HOMOs. In the ground state, it
is triplet. It may be noted that NO- is isoelectronic with 02' Thus the coordinating behaviour of NO-
is similar to that of 02.
The overlap interaction in different possible modes of ligation by O2 is illustrated in Fig. 9.13.2.
ry
o
M-O-O vs. M-O/ (cf. Fig.9.13.4)
ra
In the linear mode of coordination, the filled MO (i.e. O';(2s)) of O2 which can participate as a
ib
O'-donor orbital is of too low in energy to participate in bonding with the metal d-orbital. The
yl
n* -MOs (i.e. SOMOs) can only weakly participate in n-bonding. This is why, the linear mode of
coordination is not favoured. It may be mentioned that in the bent end-on interaction, one
m
n* -MO of O2 makes a strong a-type interaction and the other orthogonaln*-MO makes an-type
interaction. These are the favourable interactions and this mode of coordination is very often
he
found.
lc
(B) Linear mode (cf. Fig. 9.13.4): n;-MOs (Le. SOMOs) of O2 can equally carry out a 1t-type
ea
interaction with the metal d-orbitals. Consequently, degeneracy of these two n*-MOs is not disturbed.
These n-interactions are:
th
7t-interaction: n g*(2px) ± dxz ; n;(2py) ± dyz

e/
The a;(2s) (filled) and a;(2pz) (vacant) of O2 can carry out a a-type interaction with the metal
d z2 orbital. Thus the a-interaction is:
t.m
o-interaction: O';(2s) and a;(2pz) with d Z2 •

This gives a very poor interaction and the metal d Z2 orbital remains practically nonbonding (with
e
some antibonding character) (cf. Fig. 9.13.4). These aspects have been discussed later. However, this
er
linear mode of binding is not known in the real examples.
(C) Bent mode: If one n;-MQ~f O 2 makes a a-type interaction with the metal d Z2 orbital then the
H
other orthogonal (.1) n* -MO of O2 makes. a poor 1t-type interaction with the metal dyz orbital. In this
k
event, the metal dX)., d X2 _ y2 and dxz orbitals remain as the nonbonding ones.
lic
n;(2p) ± d Z2 (o-interaction); n; (orthogonal, 2p) ± dyZ (1t-interaction); dxy, d x 2 _ 2 ,dxz (nonbonding)

y
C
(cf. Figs. 9.13.2-3).

Very often, O 2 binds in this bent end-on fashion as in hemoglobin (Hb-Fe II ), myoglobin
(Mb-Fe II ), and in many other Fe(II), Co(ll) complexes.
There are many views to interpret this mode of coordination. It is evident, that in the interaction with
the metal d-orbitals, the fate of the n* -MOs (i.e. SOMOs) is changed: one makes a good a-type inter-
action while the other makes a poor n-interaction. The n* -MO making the a-type interaction with the
metal d Z2 orbital is stabilised more. Thus, their degeneracy is lost and triplet O 2 becomes singlet
02' Le.
---4- ---4- -------..

(Bent mode of
coordination)
<:I (rr)
~E
(LUMO)
> pairing energy (P)
( ' - - - - - - ------") (HOMO)

y (cr)
SOMOs, rr*-MOs
ry
(Singlet 02)
(Tri plet 02)
ra
The electron pair in the n*-MO (HOMO) of the singlet O 2 can be used for a-donation and the vacant
n*-MO (LUMO) nlay be used to function as a n-acceptor orbital. In this mode of coordination, it has
ib
been found that the metal centre undergoes Ie oxidation giving rise to superoxide (0 2-), i.e. MX+ + O 2
~ M(x+1)+ - O 2-. The n-acceptance in the singlet O 2 may lead to this superoxide formation. However,
yl
this bent mode of coordination leading to the superoxido complex can be best explained in terms of the
m
molecular orbital picture of the L sM(02) adduct (Fig. 9.13.3). It is evident from this picture that the
lower MOs which are filled in are preferably enriched with the character of the n*-MOs of O2. It
he
explains the electron flow from the ~etal centre to the coordinated O2 (i.e. oxidation of the metal
centre and reduction of O 2). This is equivalent to oxidative addition.
lc
• Electronic configuration ofHb - O2or Mb - O2(i.e. LsFeII - 02): n(dyz ' n*)2 a (d .. 2 , 1t*)2 nb(dxz )2
ea
nb(dxy )2 (low-spin) (8 1,82 ) P). "
• Electronic configuration of [CoII (B)(02)(salen)]: n(d yZ ' n*)2 a (d .. 2 , 1t*)2 nb(dxz )2 nb(dxy )2
th
n*(d.yZ' n*)1 (low-spin) (8 1 ) P). . " .

e/
t.m
-------------- ..... - - - - -
e
er
HOMO
H
k
lic
I0 Oxygen atom I
C
rr(d yz ' rr*)
(a) (b)
Fig. 9.13.3 (a) Bent end-on bonding 'leading to a-type interaction in LsM02 • (b) MO picture of LsM - 0
, ~
(The energy differences denoted by ~1~;~2' ~3' ~4 are not in scale). 0
• Electronic configuration of the brown ring complex: Assuming [Fe III (NO-)(OH2)s]2+ to represent
the brown ring complex, th~ electronic configuration may be expressed in terms of the MO-diagram (cf.
N0- and O 2 are isoelectronic):
n(d.vz ' n*)2 cr (d Z2 , 1t*)2 nb(dxz ) 1 nb(dx.J 1 n*«((.. Z, n*)1 (intermediate spin)
(~b ~3' ~4 ( P but ~1 ) P; cf singlet O 2 being a better n-acceptor than singlet NO- is a stronger
field ligand than NO-)
It explains the magnetic property of the brown ring complex (s =%).
ry
(D) NO- vs. O2 as the ligands and brown ring complex: Though NO- and O 2 are isoelectronic but
ra
NO- is a very much weaker n-acceptor ligand (cf singlet NO- vs. singlet O 2) because it is already
negatively charged. Besides this, N is less electronegative than O. Thus, for NO-, the crystal field
ib
splitting is less and the remaining aqua ligands are also the weak field ligands. Consequently in the
yl
brown ring complex, complete spin pairing (leading to S = 1/2, in terms of Fig. 9.13.3) is not attained.
It attains the intermediate spin pairing condition. It may be noted that the strong n-acceptance will
m
lower the MO, n(dyz ' n*) (cf Fig. 9.13.3) and raise the MO, n*(dyz ' n*) in terms of energy (i.e. ~2
becomes larger to favour the spin pairing).
he
Here it is important to mention that when NO binds in an angular fashion (i.e. M - N ), it is
lc ~
o
ea
not necessary to consider to start with NO as NO-. The (Fe - NO) 7e- system (the sum of metal
d-electrons and n*-electrons of NO = 7) in terms of the Fe - N bent linkage, places the electrons
th
" o
e/
t.m
Mx+ + O2 ----.. M-O~ i.e., M(X+1)+-0;

.... ~O
0--0 = 125 -135 pm ;
(11 1- 0 ; )
Common Observation
(superoxido complex) v o - o = 1130 - 1195 cm- 1
e
(x+2)+ 0
er
----.. M/ I
"0 i.e., M(X+2)+-0;-
H
0--0 = 130 -155 pm ;

(112-0:-) vo - o =800 - 930 cm- 1
k
(peroxido complex)
lic
C
/O~/M
M '0 0 - 0 = 126 -136pm, cf. In free O2 as in K0 2 :
vo-o =1075-1125cm- 1 0 - 0 = 128 pm, vo- o = 1145 cm- 1
(Jl-11 1 : 111-0;)
/O"",/M 0-0 = 144 -149pm, In free O~- as in Na 2 0 2 :

M 0
vo-o = 790 - 885 cm- 1 0-0=149 pm,vo_o = 842 cm- 1
(Jl-1l 1 : 111-o~-)
in the MOs (specially the low energy MOs, Fig. 9.13.3) which are enriched with the character of the
n* -MOs of NO. It leads to the electron flow from the 'metal to the ligand NO. It explains the
formation of [Fe II1 (NO-)(OH 2)s]2+ from the interaction of NO with [Fe(OH 2)6]2+, i.e. oxidation of the
metal centre and reduction of NO.
(E) Linear coordination (M-O-O) vs. bent coordination [M- o'\.oj by O2 and comparison
ry
ra
of the coordinating modes of O 2 (n*2), NO (n*l) and CO (n*o): Fig. 9.13.4 qualitatively describes the
MO energy levels for the LsFelI-O-O and LsFe ll - 0
ib
linkages. In the linear mode, two electrons
"
yl
o
m
are placed in the nonbonding d Z2 orbital which is weakly antibonding. In the bent coordination mode,
the d: 2 orbital is stabilised through an efficient a-interaction. Thus, placement of electrons in the
he
L Fell - 0 linkage is relatively favoured.
5 "
o lc
ea
Now let us compare the coordinating behaviours of CO, NO and O 2 having 0, 1 and 2 electrons in their
respective n* -MOs. If we consider that the MO energy diagram (Fig. 9.13.4) is approximately
th
e/
- - - - - - - - - - - - - - - ------'If-
t.m
e
er
H
k
lic
0 Q) ~-- .. x
C
0>
I as
~
~
0 y
I
LsFe
Ci;
Q)
c:
2.
Fig. 9.13.4 General MO energy diagram for [L_M-X-Y] (linear mode of coordination) and [L 5 M - X ] (bent
) ~
Y
mode of coordination) for X-Y = CO, NO and 02 (Illustrated for (heme)Fe Il - XY, i.e. (heme)Fe Il - 02 interaction in
the drawing for an example).
applicable for LsFeII-CO, LsFeII-NO and LsFe ll - O 2 then for their linear modes of linkage, the
d Z2 orbital (which is weakly antibonding) bears the electron(s) as follows:
X-V: co NO O2 ]
II
[LsFe -X- Y J: o (Zero)
"----v--'
~ Assuming the low-spin configuration.
ry
d,:2 as LUMO d,:2 as HOMO
ra
(Note: For the linear linkage, the nonbonding d Z2 orbital is weakly antibonding because it weakly
interacts with the deeply seated a*2(2s) orbital of O 2- In this interaction, a*(2s) of O 2 slightly goes down
ib
and d Z2 (M) slightly goes up. This is not shown for the sake of simplicity).
yl
Thus for the linear mode of linkage of CO, no destabilisation occurs but for the linear linkage by NO
and O 2, the destabilisation prevails. But, if NO and O 2 make the bent linkage, the HOMO bearing 1 and
m
2 electrons respectively is a nonbonding MO. This is why, hemoglobin (Hb) forms a linear linkage
with CO while under the comparable condition, NO and O2 make a bent linkage with hemoglobin.
he
(Note: Energy of the n*-MO of CO, NO and O 2 follows the sequence: CO ) NO ) O 2, It indicates that
the ease of reduction of these ligands (i.e. electron flow from metal to ligands into the respective
lc
n* -MOs) occurs in the sequence: O 2 ) NO ) CO. In fact, in the bent linkage formed by O 2 and NO, they
remain as O 2- and NO-.)
ea
(F) Perpendicular mode: Fig. 9.13.5 indicates that the filled n u (2pJ of O 2 makes a a-type interaction
with the metal d Z2 orbital. The filled orthogonal <-i) n-BMO, i.e. n u(2p y) of O 2 can make an-type
th
interaction with the metal dyz orbital. But energy of these x-BMOs is too low (compared to those of
n;
e/
the metal d-orbitals) to make any effective interaction with the metal d-orbitals. The (2p) orbital of
O 2 can make a very good x-type interaction with the metal dxz orbital. Another orthogonaln*-MO, i.e.
t.m
n;(2P.J can make a relatively weaker &.type interaction with the metal dxy orbital. Thus in these orbital
interactions, the d x2 _v 2 orbital remains nonbonding. Considering the energy difference between the
n- BMOs of O 2 and metal d-orbitals, the metal d Z2 and dyZ orbitals may be approximately considered to
e
remain as the nonbonding orbitals also. Thus the important orbital interactions are:
er
x-type interaction n u(2py)(02) ± dyz(M) (very weak interaction)

H
a-type interaction n u(2pz)(02) ± d Z2 (M) (very weak interaction)

(Fig. 9.13.5)
x-type interaction n;(2Pz)(02) ± dxiM) (strong interaction)
k
&.type interaction n;(2P.. )(02) ± dxy(M) (relatively weak interaction)

lic
"12-02 vs. "12_C2H 4 : Coordinating behaviour of 112-C2H4 is totally different from that of 112-02' The
C
n-BMO of C 2H4 can make a a-donation as its energy is comparable to that of the metal d-orbital. For
O 2, the energy of its n- BMOs is too low to interact with the metal.
The n*-MOs of O 2 interact with the metal d-orbitals in different ways. Thus degeneracy of the
n*-MOs of O 2 is destroyed and the triplet oxygen becomes the singlet oxygen, i.e.
Perpendicular
co~~~~a~:on 11~8) LUMO [ng*(2py)]
--1- --1- (Fig. 9.13.5)
~ - - - - {', ~E > pairing energy
HOMO [n~ (2pz)]

(n)
ootB (d )
ry
yz 1t u(2p y)
dz2(M) - 1tu (2Pz)(02)
ra
i.e., 1t 1l - M (a) d yz (M) - 1tu (2py)
(a-type interaction) i.e.,1t.L-M (1t)
ib
(1t-type interaction)
(a) x (b)
yl
• denotes O-atom I
m
J - - - -. . Z
he
lc
ea
th
1t; (2p y) (02)

d xz (M) - 1t; (2Pz)(02)
e/
(1t-type interaction) d xy (M) - 1t~(2py)(02)

1t~-M (1t)
t.m
(a-type interaction)
(c) 1t:- M (8)
(d)
e
Fig. 9.13.5 Different possible orbital overlap interactions in the perpendicular mode of coordination by dioxygen (i.e.
02) Note: The 1t-BMOs, i.e. 1ti2py, z) are of very low energy compared to the metal d-orbitals. This is why, the (a) and
er
(b) interactions are very weak
In this condition, one n* -MO acting as a HOMO can function as the n-donor orbital while the other
H
n* -MO acting as the LUMO can function to receive the electron from the metal centre through
8-bonding. It explains the 7t-acidic character (more correctly, ~-acidic character) of dioxygen in this
k
mode of ligation. In other words, if a complete MO diagram is drawn by considering the said 7t- and
lic
~-interactions then the lower BMOs enriched with the character of n* -MOs of O 2 are filled in. It is
equivalent to the electron flow the from the metal to the coordinated O 2 , In other words, it may be
C
described as the oxidative addition.

(G) Bonding in the dioxygen adduct ofVaska's complex: Now let us try to understand the bonding
interactions in the dioxygen adduct of Vaska's complex where O 2 binds as 112-02 (i.e. perpendicular
mode).
I
trans- [Ir (CO)CI(PPh 3)2 ](16e) + O 2 ~ trans- [IrII(CO)CI (11 -0 2)(PPh 3)2]
2
(yellow) (orange)
The reversible oxygen binding gives a dimagnetic orange coloured compound when O 2 is bubbled
into a benzene solution of the Vaska's compound, [Ir(CO)CI(PPh3)2] (yellow). The coordinated dioxygen
can be released by simply passing N2 gas through the orange coloured solution. This reversibe
02-binding is quite important from the standpoint of synthetic oxygen carriers. In the dioxygen adduct,
0-0 bond is perpendicular to the P-Ir-P trans-pair of axial bonds; CO, CI and mid-point of the
0-0 bond are the corners of a trigonal plane (ef Fig. 9.13.6). The observed 0-0 distance (= 130 pm)
and v o- o ::::: 860 cm- I in the adduct indicates that O 2 remains as O 2- (ef 0-0 bond length in free
superoxide = 128 pm). Thus the complex is: [IrII (CO)CI(11 2-02)(PPh 3)2]. The unpaired electron oflr(ll)
ry
(d?) remains in an antiferromagnetic coupling with the unpaired electron of superoxide
(0 2 ) to generate the diamagnetic behaviour of the adduct. The higher veo value (= 2015 cm- I ) in the
ra
adduct compared to that of the free Vaska's complex (v eo = 1967 cm- I) indicates the more positive
oxidation state of Ir in the adduct.
ib
J-----:'"
PPh 3 Note: This discovery by
yl
o ---- L. Vaska (1963) created
~Ir/CI
-CI
E>I~CI
3
a tremendous excitement
m
Ph PP ] + 02
among the chemists to
~PPh
[ OC/
o-------~------~.Co
he
3 understand the proper-
(Yellow)
ties of oxygen-carrying
PPh 3
metalloproteins.
(Orange)lc
ea
Fig. 9.13.6 Formation of the dioxygen adduct in a reversible reaction reaction with Vaska's complex.
For the corresponding iodido complex, i. e. [Ir(CO)I(PPh 3)2] the dioxygen adduct,
th
[lr(CO)I(112-02)(PPh3)2] shows the 0-0 bond length 151 pm (ef 0-0 bond length in free peroxide,
0i- = 149 pm). It indicates that the complex is: [lrIlI(CO)I(112-0i-)(PPh3)2]. It indicates that compared
e/
to the chlorido-complex, in the iodido-complex, the electron flow from the meal to the n*-MO of O 2
through 8-bonding is more pronounced. It is reasonable because chlorine is more electronegative than
t.m
iodine aI).d ,this is why, in the chlorido complex, the electron flow from the metal to the O 2 is restricted
more compared to that in the iodido complex. It explains that the B-bonding interaction is stronger
in the iodido complex. In fact, the Ir-02 bond is much stronger in the iodido complex. This is why,
e
O 2 binds irreversibly with the iodido complex but reversibly with the chlorido complex.
In terms of MOT, it has been already mentioned that the lower BMOs are mainly enriched with the
er
character of the n* -MOs of O 2, i.e. electron flow from the metal to the coordinated oxygen (0 2). The
H
AO of I is more diffused compared to that of Cl. Thus, in the Ir-I bond, the overlap is relatively
inefficient compared to that in the Ir-CI bond. This makes the Ir-orbital more available for inter-
action with the 1t*-MOs of O 2 in the iodido complex. In fact, the Ir-0 2 bond is much stronger in the
k
iodido-comp1ex compared to that in the chlorido complex. This fact has been explaind already in terms
lic
of the better B-back bonding (i.e. B-acidity of ,,2_02) in the iodido complex. The better interaction of
the Ir-orbital with the n* -MOs of O 2 leads to the more electron flow to the n* -MOs of O 2 because the
C
filled in lower BMOs are mainly enriched with the character of the n* -MOs of O 2. It explains the higher
electron density in the n*-MOs of O 2 in the dioxygen adduct of the iodido complex. This explains the
existence of 01- in the iodido co~plex while Oi in the chlorido complex.
Some authors explain the observation by considering the oxidative addition of O 2 to [IrX(CO)(PPh 3hL
i.e. the product is an adduct of 01- (peroxide).
[lrI(CO)X(PPh 3)2] + O 2 ~ [lr IIl (CO)X(1l2-0i-)(PPh 3)2].
(X = CI, I)
In 01-, both the n*-MOs are filled in but one n*-MO can make a n-type interaction with the metal
d-orbital while the other orthogonaln*-MO can make a 8-type interaction (i.e. delta-acidity) with the
metal d-orbital (Fig. 9.13.5). The filled n*-MO which can make a n-type interaction acts mainly as the
donor MO. This donation to the metal is better for the chlorido complex because of the higher
electronegativity of chlorine. This higher depletion of electrons from the n* -MOs of 0l- to Ir(lll)
finally leads to IrII - O 2 in the chlorido complex.
• [lr(CO)X(PPh 3)2] binds O 2 reversibly (for X = CI) and irreversibly (for X = I, CH 3)-why?
ry
• [lr(CO)2X(PPh3)2]: stability order, X = I ) CI, why?
ra
• In [lr(CO)CI(PPh3)2(,,2-02)](tbp), PPh 3 groups are in the axial directions while in
[lr(CO)CI(PPh 3)2(,,2-C 2X 4 )] (X =F, CN), the equatorial positions are occupied by 2PPh 3 groups
ib
and 112-C2X 4-why?
(ef n-acceptor strength: C 2X 4 ) CO ) PPh 3 ) ,,2-0 2)
yl
(H) O 2 as a bridging ligand: O 2 can act as a bridging ligand in many ways. The J.l-02 moiety may
m
remain as J.l-02- or J.l-Ol- depending on the conditions.
he
2-
2LsMII + O2 ----3~~ LsMIII_O", (i.e. 1l-l]1: l]1 - O2 )
O-M1IIL s , M = Co, Fe.

lc
However, for some cases of Co(II), the bridging moiety may be superoxide (i.e. Jl-"l : ,,1--0 2)
ea
~O~
th
2(L)Cu l + 02 ~ (L)Cu"-O, Or(L)cJ~ I Cu"(L)

~ o/.(/ _
e/
'0 C II(L)
- u 2·
f.l 11 . II
2-0 2-)
2
t.m
1l-l]1 : l]1_0:- i.e. 1l-1, 2-0t ~
o
II~~
(L)CU~
e
"'-..Culll(L)
0/
er
The peroxido-bridged Cu(II) complexes are of biological relevance (e.g. hemocyanin, tyrosinase,
H
etc.) (see the author's book, Bioinorganic Chemistry).

k
9.14 DIFFERENTTYPES OF ORGANOMETALLIC COMPOUNDS OFTHE MAIN GROUP

lic
ELEMENTS AND TRANSITION METALS

A. Main Group Elements: Alkyl and aryl compounds are the important examples for the main group
C
elements (e.g. Li, Mg, B, AI, Si, Ge, P, As, Sn, Pb, etc.) and the Gr. 12 metals (i.e. Zn, Cd, Hg).
B. Transition Metals: The alkyl and aryl complexes of the transition metals are only stable under some
special circumstances. Other types of stable organometallic compounds of the transition metals are:
• alkene complexes: alkenes with the unconjugated double bonds can form the metal-carbon linkages;
conjugated double bonds can also participate in the metal-carbon bond formation.
• alkyne complexes: like the olefinic linkage, the acetylinic linkage can also participate in metal-
carbon bond formation.
• complexes of delocalised carbocycles: such carbocyclic groups act as the n-donor ligands. Im-
portant examples of such ring systems are given in Fig. 9.14.1.
'- -' l2-

UI
\
'
, ... _, ' '
ry
ra
10e donor
ib
Fig. 9.14.1 Examples of some representative carbocycles having the delocalised n-electron clouds
yl
• allyl complexes: ally radical can act as a three-electron n-donor.
• carbene and alkylidene complexes
m
• carbyne and alkylidyne complexes
he
9.15 ORAGANOMETALLICS OFTHE MAIN GROUP AND ZINC GROUP ELEMENTS
These are mainly the alkyl and aryl compounds. The M-R or M-Ar bonds are basically the a-bonds.
lc
• M-C bond strength: In general, the bond strength decreases for the heavier congeners. This is
illustrated. B-C ) AI-C) Ga-C ) In-C; Si-C ) Ge-C ) Pb-C; As-C) Sb-C ) Bi-C.
ea
• Carbanionic character in the M-C bond: The M-C bond is polarised to induce the carbanionic
character. The more electropositive metal introduces the more carbanionic character. Hydrolytic cleavage
th
is favoured for the more carbanionic bond which experiences the prototysis easily. Besides the protolysis
of the M-R bond, nucleophilic attack on M is also required for the hydrolytic cleavage of the M-R
e/
bond (cf push-pull effect, cf Chapter 10, Vol. 2). The nucleophilic attack is favoured for the til' \1\'
electropositive metal centre producing the more polarisation in the M-C bond.
t.m
• Inflammable character: Organometallics of more electropositive metals, e.g. LiR, ZnR~, .\ II~ "
etc. burn in air on heating. Such organometallics or their dissociated products possess the \ d(dlJI
orbitals.
e
• Re~ucing character: Organometallics (specially of more electropositive Inetals) act as the reduc-
er
ing agents and the organic moiety is oxidised. Al 2Me6 is a good reducing agent and it is used in the
synthesis of carbonyls through the reductive carbonylation.
H
9.15.1 Synthesis of the Alkyl or Aryl Compounds

k
These are prepared as follows:

(i) Reaction of the active metals with the alkyl halides:
lic
2M + RX ~ M-R + MX,
2Li + CH 3CI ~ Li-CH 3 + LiCI
C
Mg + CH 3 Br Et~O )CH 3 MgBr (Grignardreagent)

Reactivity order: RI ) RBr ) RCI » RF; allyl or benzyl halide) RX ) ArX
The reactivity order can be explained in terms of the C-X bond strength.
Note: High reactivity of RI can lead to coupling of organic groups.
RI + 2Na -7 RNa + Nal, RI + RNa -7 R-R + Nal
(cf. Wurtz reaction producing alkane, Fittjg reaction producing aromatic hydrocarbons.)
(ii) Transmetallation: Replacement of a metal in an organometallic compound by a more electro-
positive metal, i.e. M + l\1'R ~ MR + M' where M is more electropositive than M'.
Mg + Hg(CH 3)2 ~ Mg(CH 3)2 + Hg

Be + Hg(CH 3)2 ~ Be(CH3)2 + Hg
2Ga + 3Hg(CH3)2 ~ 2Ga(CH 3)3 + 3Hg
2K + HgR 2 ~ Hg + 2K+ R-
(iii) Metathesis, i.e. double displacement: Double displacement between an organometallic com-
ry
pound and a halide, e.g.
3GeCl 4 + 2AI 2(CH 3)6 ~
3Ge(CH3)4 + 4AICl 3
ra
2LiC 6H s + BeCl 2 ~ Be(C 6 H s)2 + 2LiCI
ib
MX 2 + 2CH 3MgBr ~ M(CH 3)2 + MgBr2 + MgX 2
yl
(M = Zn, Cd, Hg).
By using the metathesis reaction, the alky or aryl compounds of Gr 13, 14, 15 elements can be
m
easily prepared.
he
SiCl 4 + (LiMe)4 ~ SiMe4 + 4LiCI
2BX 3 + ( AIMe3)2 ~ 2BMe3 + 2AIX 3
lc
The halides move towards the more electropositive centres while the alkyl groups (as R-) move
towards the more electronegative centre where the covalent interaction is better.
ea
(iv) Hydrometallation: Addition of an M-H bond to a carbon-carbon double bond.
Et 2AI-H + H 2C = CH 2 AIEt 3
th
-----t
H 3Si-H + H 2C = CH 2 -----t EtSiH 3 (Hydrosilylation)

e/
Me3Sn-H + H 2C = CHC0 2Me -----t Me3Sn-CH2CH2C02Me

t.m
The higher bond energy of the C-H bond cOlnpared to that of the M-H bond is the driving force
of the reaction.
(v) Metallation: Protonic hydrogens of hydrocarbons may be replaced by metals.
e
Ph 3CH + CH 3 Li -----t Ph 3CLi + CH4, 2C sH 6 + 2Na -----t 2Na+C sH s- + H 2

er
2CH 3COCH 3 + Hg[N(SiMe 3 )2] "-----t 2NH(SiMe 3 )2 + Hg[MeC(O)CH 2]2

H
9.15.2 Structure and Properties of the Organometallics of Alkali Metals

k
Alkyl or aryl compounds of the highly electropositive metals (i.e. Na to Cs) are ionic while those of
lic
lithium are the typically covalent compounds.

(A) Ionic organometallics: Examples of ionic organometallics are Na+CsH s-, Na+(Ph 3 C-),
Na+(CIOHi), etc. where the carbanion is stabilised through conjuation. Sodium naphthalide is pre-
C
pared as follows:
C)OH g (nephthalene) (dissolved in THF)~Na[C)()HgJi.e. Na+(CIOH x)-
We_
+ +
H Na
H H
~ ~
~ I // ~ I
• .....H
ORGANOMETALLICS AND METAL CARBONYLS: n-AciD METAL COMPLEXES 1403
Sodium cyclopentadienide can be prepared as follows:
C SH6 (dissolved in THF)~Na[CsHsJi.e. Na+CsH +.!H 2 s 2

Stability of the radical anion like naphthalide: The unpaired electron in naphthalide (CIOH g-)
resides in the LUMO (i.e. n*-MO) of naphthalene. Formation of such carbanions, i.e. radical anions, is
ry
favoured if the LUMO is of low energy. With the increase of conjugation, energy of the LUMO de-
creases (ef particle in box model). The ease of radical anion formation thus follows the sequence.
ra
anthracene) phenanthrene) naphthalene) biphenyl) benzene
ib
increasing extent of conjugation, decreasing trend of energy of the LUMO
and increasing trend of reduction
yl
It has been experimentally found that the more conjugated arenes form the alkali metal salts
m
more easily. Because of the extensive delocalisation of the negative charge over the whole skeleton, the
effective radius of the anion is very large. Consequently, the electrostatic attraction between the cation
he
and anion in the salt is not very_high and they are soluble in the solvents like ether. Such alkali metal
salts are widely used as the reducing agents. In many aspects, they are better than sodium itself as the
lc
reducing agents. Unlike sodium, its such salts are readily soluble in the solvents like ethers. It is easier
to control the homogeneous reactions. Moreover, their reducing power can be monitored by varying the
ea
radical anions.
(B) Organolithium compounds: The alkyl or aryl compounds of lithium are the typically covalent
th
compounds. They are generally liquids or low melting solids. They are soluble in the nonpolar hydro-
carbon solvents. On standing, they slowly decompose to LiH. However, LiMe, LiBu t and LiBu n are
e/
relatively stable. The lithium alkyls are commercially very important. They are prepared as follows:
t.m
Li + RCI ~ LiR + LiCl (in solvents like toluene, cyclohexane, light petroleum, etc.)
(C) Structural features of LiCU3 : Lithium alkyls are generally tetrameric or hexameric. LiCH 3
exists as (LiCH 3)4 where the four Li atoms occupy the corners of a tetrahedron. Above the each trigonal
e
face, there is a methyl group. Thus the C-atom of a methyl group binds with the three Li-centres at the
corners of the trigonal face. By considering the positions of 4 Li atoms and 4C-atoms, a distorted cube
er
can be constructed where the Li and C atoms occupy the alternate corners of the cube. The Li-C
distance is 231 pm and the Li-Li distance is 268 pm. In the (LiCU3 )4 clusler, each Li atom and each
H
C-atom is considered to be sp3-hybridised. By using the three sp3-hybrid orbitals, three C-H 2c-2e
bonds are produced. The remaining sp3-hybrid orbital is engaged in bonding with the three Li-atoms on
k
a trigonal face. It involves the 4c-2e bonding in each Li 3 C unit. Thus, the 4-electron pairs
lic
(= 4e from 4 Li atoms + 4e from 4C atoms) are utilised to produce the tetrameric (LiCH 3)4 cluster unit.
This is shown in Fig. 9.15.2.1.
C
However, in the crystalline state, the (LiMe)4 clusters are interconnected along the cube diagonals by
using the bridging CH 3 groups. In fact, the methyl-C aton1 binds simultaneously with the three intra-
. cluster Li-atoms and one intercluster Li atom. Thus, coordination number of C is 7 (= 4 Li + 3 H).
Similarly, each Li-centre simultaneouly binds with the three intracluster Li-atoms, three intracluster
C-atoms and one intercluster C-atom. This leads to 7 coordination number of Li. Some authors have
argued that the Li-atom not only binds to the intercluster C-atom of the bridging Me-group but also
with the three H-atoms (i.e. agostic interaction) of the bridging Me-group. It is believed that the
C-H---··Li agostic interaction is playing an ilnportant role in determining the crystal structure of
(LiMe )4. It leads to 10 coordination number to Li, i. e.
lOC.N.= 3Li+3C + lC+3H

~ ~
Intracluster Intercluster
-----ABMO
ry
-----NBMO
ra
ib
--%--BMO
yl
"------------.............---------)
m
(c)
he
(Intracluster distance)
268 pm
~
lc
ea
th
Li
236 pm
e/
:.c 231 pm
H
(intercluster
distance)
t.m
(intracluster
distance)
(d)
~
. Agostic interaction
e
231 pm (229 pm)

er
,H
H
" H
',,"
k
lic
268 pm
c \ . 231 pm
C
(intracluster
distance) (intracluster distance)
(e)
Fig.9.15.2.1 Crystal and Inolecular structure of (LiMe)4 : (a) and (b) Unit cell of Li4Me-l; (c) Bonding and formation
of 4-centred MOs on a tetrahedral face-giving rise to 4c-2e bond; (d) 7 coordination number around the C-atom;
(e) 10 coordination number around the Li-atom after considering the agostic interaction.
The structural parameters are:

Li-Li (intracluster) = 268 pm,
Li-C (intercluster) = 236 pm,
Li-C (intracluster) = 231 pm,

Li - C- Li (intracluster) = 68°
Li-H (intercluster, = 229 pm
agostic interaction)
The proposed agostic interaction is more pronouned in the crystal structure of (LiEt)4 where the
Li-H distance (intercluster agostic interaction) is close to 198 pm which is less than the Li-H
ry
distance (::::: 204 pm) found in solid LiH.
ra
To attain the 7 coordination number of C, it uses its three Sp3 hybrid orbitals to produce three
2c - 2e C-H bonds and the remaining Sp3 hybrid orbital is used for binding simultaneously with 4 Li-
ib
atoms (3 intracluster and 1 intercluster) through the formation of 5-centred MOs.
(D) Structure of hexameric lithium alkyl, i.e. (LiR)6: The bonding in the tetrameric cluster (LiR)4
yl
e.g. (LiCH 3 )4 has been discussed. LiR sometimes may produce the hexameric cluster (LiR)6' LiEt when
m
dissolved in hydrocarbons produces the hexameric cluster unit (LiEt)6 in which 6 Li-atoms are placed
at the comers of an octahedron and 6 Et groups are placed above the six faces of the eight faces of the
he
octahedron. It also experiences the multicentre bonding.
(E) Breaking of the associated structure of LiR or LiAr: They generally remain as the associated
aggregates like tetramer, hexamer. However, in presence of the inert coordinating ligands (which do
lc
not allow protolysis because of the absence of even weak A-H acidic functional group) like tmda, i.e.
ea
N, N, N', N'-tetramethylethylenediamine (having no N-H group), the higher aggregates may break
down. For example, LiPh gives [Li 2(Ph)2(tmda)2]'
th
e/
t.m
e
er
Note: The metal-carbon bonds (i.e. M-C) are polarised as McS+_C cS- to induce the carbanionic char-
H
acter on C. For the more electropositive metal, this charge separation is more to produce the more
carbanionic character in the M-R bond. Carbanionic moiety (i.e. R- or Ar-) of the p-block
k
organometallics can extract proton even from the mildly acidic A-H functional groups. Thus any
lic
ligand to stabilise such organometallic compounds must lack in such acidic protons. In fact, the A-H
functional group leads to protonolysis or protolysis of the carbanionic moiety. When the carbanionic
C
character is significatly large, the organometallics cannot withstand water or any protonic sub-
stance. This fact will be illustrated later.
(F) Reactions of alkyl lithium: In organic synthesis, (LiMe)4 and (LiBu n )4 are widely used in both
laborator~.T and industry. They are mainly used as the polymerisation catalysts, alkylating agents and
precurso Jf organometallic reagents. In many cases, the reactions are similar to those of Grignard
1 ·\' ..
reagent'·" ,orne representative examples are given below.

LiR + H+ ~ R-H + Li+
LiR + R'I ~ R-R' + LiI
LiR + X 2 ~ RX + LiX }
3LiR + BX 3 ~ BR 3 + 3LiX «(if. synthesis of alkyl complexes
4LiR + SnCl4 ~ SnR 4 + 4LiCI of transition metals; Sec. 9.16.3).
3LiR + P(OEt)3 ~ PR3 + 3LiOEt
2LiR + HgX 2 ~ HgR 2 + 2LiX
LiR + CO2 ~
ry
RC0 2Li (Li-salt of carboxylic acid)
LiR + Ar-X ~ LiAr + RX
ra
2LiR + 3CO ~ R2CO + 2LiCO
LiR + R'-CONMe2 ~ LiNMe2 + R'COR
ib
MgPh 2 + 2PhLi ~ Li 2[MgPh4 ]
yl
Li+ + RCHO+[Ni(CO)3(solvent)]
m
he
(Unstable acyl nickel cabonyl
complex formed through CO
LiR+[Ni(CO)4]
(Nucleophilic attack by R- to
-co lc insertion in the Ni-R bond)
ea
the 16e species [Ni(CO)3]
produced)
o
th
II
e/
LiX + R - C- R' + [Ni (CO)3(solvent)]

t.m
[Fe(CO)s] also reacts in a similar way. In the above reaction, the unstable acyl metal carbonyl
intermediate experiences an electrophilic attack by H+ or R'X.
Comparison of the use of RLi and RMgX in synthesis (cf. Sec. 9.15.30)
e
er
R-R' (ct. Use of Collman's reagent known as Transition Metal

.4~ Grignard Reagent, Na 2 [Fe(CO)4]' Sec. 9.4.17)
H
R'X
k
I
A-X
II H 0+ or H 0 ...
lic
A-R ..... I RLi or RMgX

3 2
RH
(A = B, Si, Ge, Sn, "---.-------r----r--"""T1---I O

C
Pb, As, etc.) 2, H3 0+

1...------... ROH
R'CHO, H 3 0+
" - - - - - - - - + RR'CHOH
R'R"CO, H3 0+
" - - - - - - - - - + RR'R"COH
Pyrolysis of methyllithium gives Li 2CH b i.e. dilithiomethane.

(LiMe)4 ~ Li 2 CH 2
If possible, LiR on heating experiences the P-H elimination to produce an olefin and LiH. This
process is industrially important for the preparation of long-chain terminal alkenes.
~
(H:J
Li -CHCH 3 --.. ~ LiH + CH 2 ===CHR
LiUCH2
ry
CH
I
R
I
ra
R
ib
yl
9.15.3 Structure and Properties of Organometallics of Group 2
(i.e. Alkaline Earth Group)
m
The procedures to prepare the alkyls and aryls of alkaline earth group have been discussed in Sec.
he
9.15.1. Except the compounds of Be and Mg, the corresponding compounds of the heavier congeners
(i.e. Ca to Ba) are predominantly ionic. The covalent compounds of Be and Mg, i.e. MR2 and MAr2 (M
= Be, Mg) are generally the low melting solids or viscous liquids. These are inflammable and explo-
lc
sively hydrolysed.
ea
MR 2 + 2H 20 ~ M(OH)2 + 2RH
In fact, MR 2 can react with any reagent having the acidic-hydrogen (even the mildly acidic A-H
group) which leads to the protolysis of R-·
th
Be(CH 3)2 + CH 30H ~ CH 3Be(OCH 3) + CH4

e/
(A) Structure of BeMe2 and MgMe2: They are as dimers (BeMe2)2 in vapour phase and polymers,
i.e. (MMe2)n in solid state. The polymeric chain structure is produced by the bridging Me group. In this
t.m
chain, each Be-centre is sp3-hybridised and each C-centre is sp3-hybridised. Out of the four sp3-hybrid
orbitals of carbon, three orbitals are involved in making three 2c-2e C-H bonds. The remaining
sp3-hybrid orbital participates in binding with two Be-centres through 3c-2e bonding. In this 3c-2e
e
bonding, 1e comes from the sp3_C centre and another electron comes from the sp3-Be centres (i.e. one
er
Be-centre provides one sp3-hybrid orbital with an unpaired electron while the other Be-centre provides
a vacant sp3-hybrid orbital). Thus, 5 coordination number is attained around the C-atom. Such electron
H
deficient bonds, i.e. 3c-2e bonds exist also in (BeH 2)x. It may be noted that BeCl 2 also exists as
(BeCI 2)n through the bridging chloride 19ands but there remains the 3c-4e Be-CI-Be bridging
linkage, i.e. each Be-CI bond is a 2c-2e bond. The 3c--4e Be-CI-Be bridge is constituted by two
k
p-orbitals of CI with 3 electrons and two sp3-orbitals of Be-atoms with one electron (see Fig. 9.15.4.1).
lic
The dimer MeBe(f.l-Me)2BeMe exists in the vapour state.

C
(a)
ABMO
NBMO
ry
ra
ib
yl
)
"------------
~
m
(b)
Fig. 9.15.3.1 Structure and bonding in (BeMe2)x' (a) Linear polymeric structure. (b) 3c-2e Bridge bond formation
he
Note: (MgMe2)x also adopts the similar structure.
The monomeric species BeR2 is linear where the Be-centre is sp hybridised but in the polymeric
lc
species (BeR 2)n, the Be-centre is sp3 hybridised. The tendency of polymerisation by using the
~I/)
(3c -
ea
electron deficient bridge bonds 2e Be - C - Be decreases when the substituents on the
bridging C-centre are large, i.e. the steric crowding leads to depolymerisation. In fact BeBu~, i.e.
th
di-tertbutylberyllium, is linear and monomeric. In presence of the good ligands (L) like R 20, NR 3, PR 3,
etc., having no protonic A-H functional group, the polymeric structure of BeMe2 undergoes
e/
depolymerisation to generate the monomeric species.

t.m
e.g.
e
er
H
k
Alkyl beryllium hydrides can exist as the dimers through the 3c-2e Be-H-Be bridges (cf
lic
Be-H-Be bridge is more efficient that the alkyl bridge, i.e. Be-R-Be).
C
(B) Grignard reagent: The Grignard reagent RMgX (R =alkyl or aryl group, X =halogen) discovered
by Grignard in 1901 finds the versatile uses in organic synthesis. For this contribution, he was awarded
Nobel Prize in chemistry in the year 1912. The reagent is prepared in the following reaction.
Mg + RX dry ether ) RMgX, (R = alkyl or aryl)
The order of reactivity is: R = alkyl) aryl; X = I ) Br ) Cl.

The reaction requires an induction period and the reaction occurs slowly in the beginning. It may
require the addition of a crystal of iodine to penetrate the protective oxide coating on the metal surface
to make the reaction start. However, the reactive magnesium may be prepared by reducing magnesium
halide (MgX 2) by potassium and use of such reactive magnesium is convenient to prepare the Grignard
reagent rapidly.
ry
Water and air must be excluded during the preparation and of storage of the reagent RMgX. RMgX
hydrolyses very rapidly.
ra
2RMgX + 2H 20 ~ 2RH + Mg(OH)2 + MgX 2
ib
(C) Basic structure of the Grignard reagent and Schlenk equilibrium: RMgX crystallised from
ether (Et20) shows a distorted tetrahedral geometry, RMgX, (Et20)2' When crystallised from THF, a
yl
distorted trigonal bipyramidal geometry is obtained.
m
08
R
I/OC Ha
he
4
THF=
HaC40-M9",
I lc
OC 4 Ha (OC 4 Ha = THF)
X THF> Et2 0
ea
(basicity)
Thus the basic structure is RMgX· n(solvent).

th
In solution, different species may remain in an equilibrium (called Schlenk equilibrium) as follows:
e/
t.m
The position of the equilibrium depends on the nature and size of R, nature of the bridging X, and
e
coordinating power of the solvent. Dilute solution predominantly contains the monomeric species.
The solvents which can better compete as the ligands favour the solvated ITIonoI11eric species,
er
RMgX· n(solvent).
H
Existence of the species MgR 2 and MgX 2 in the Schlenk equilibrium is evidenced by the following
observation.
k
RMgX (in ether solution) dioxane) Precipitate + Filtrate.

lic
Precipitate is solvated MgX b i.e. MgX 2(C 4H s0 2)2

Filtrate on evaporation gives MgR 2
C
(D) Synthetic uses of Grignard reagent: Only some representative examples are given below.
(i) Primary alcohol synthesis:
0., RMgX
RMgX --=-------7 ROOMgX )2ROMgX
V
RMgX-----::o::....----+) RCH 2 CH 2 0MgX
HCHO
RMgX
(ii) Secondary alcohol synthesis:
RMgX + R'CHO ~ RR'CHOMgX
(iii) Tertiary alcohol synthesis:

RMgX + R'R"CO~RR'R"COMgX_H_+~) RR'R"COH
H 20
ry
(iv) Carboxylic acid synthesis:
ra
(v) Aldehyde synthesis:
ib
RMgX (i) HC(OEth ) RCH(OEt)2
yl
(ii)H+
m
(vi) Ketone synthesis:
RMgX+R'CN~[RR'C=NMgX]_H_+--+)RR'CO
he
H 20
(vii) Ester synthesis:
RMgX + R'OCOCI~[RC(OR')CI(OMgX)J-:'-~--+) RC0 2R' lc

ea
(viii) Primary amine synthesis:
RMgX + CINH 2 ~ RNH 2 + MgCIX; RMgX + MeONH 2 ~ RNH 2 + MeOMgX

th
(ix) Synthesis of different types organo-compounds:

e/
S H+ RMgX
RMgX ~ RSMgX H 0) RSH ; RSMgX ) R 2S + MgX 2 + Mg
2
t.m
R'X ,
RSMgX----+) RSR + MgX 2
H+ I.,
RMgX -H-20~) RH ; RMgX ~ RI
e
er
RMgX )BeR 2 ; RMgX BCl 3 ) BR

3
H
SiC1-t (
RMgX ) RxSiCl y x + y = 4 ) ; RMgX SnC1-t
) SnR 4
RxSiCl y (i.e. alkyl or aryl chloro-silanes) are important in the manufacture of silicones.
k
Note: Beryllium Grignard reagent RBeX is less reactive than RMgX· RBeX can be prepared as follows:
lic
BeMe2 + BeCl 2 ~ 2MeBeCl.

(E) Alkylmagnesium alkoxides (RMgOR'): These are closely related to Grignard reagent. These
C
are prepared as follows:

R'OH , R'CO
MgR 2 (-RH) RMgOR ; MgR 2 2 ) RMgOCRR;
Like RMgX, RMgOR' remains associated and the degree of association depends on the nature of
solvent. In the strongly coordinating solvents like THF, they remain as the dimers by using the
f.l2-0R' bridges. On the other hand, in the weakly coordinating solvents, they can exist as the linear
oligomers by using the f.l2-R and f.l2-0R' bridges or as cubanes by using the f.l3-0R' bridges. However,
for the bulky R'-groups, RMgOR' tends to remain as the dimers even in the weakly coordinating
solvents like Et 20. These are illustrated in Fig. 9.15.3.2 for MeMgOR'.
ORGANOMETALLICS AND METAL CARBONYLS: n-AclD METAL COMPLEXES 1411
ry
ra
(a) Solvated dimer, i.e. (MeMgOR'·Sh (in a good coordinating solvent, S).
ib
yl
m
he
R' R'
lc
ea
th
e/
(b) Unsolvated linear oligomers; different isomers depending on the nature of the bridges, i.e.
t.m
e
er
R'
H
k
lic
C
(c) Unsolvated cubane tetramer (MeMgOR')4 using the J.l3-0R' bridges.
Fig. 9.15.3.2 Structures of associated MeMgOR'. (a) solvated dimeric structure in the good coordinating solvents like
THE (b) and (c) Polymeric structure in the weakly coordinating solvents like Et 20.
(F) Bis-cyclopentadienyl compounds: Some of them are quite interesting in terms of their structural
characteristics. They are prepared as follows:
Mg soo~~oc >[ Mg(TJS-CSHS)zJ+ H 2
M+Hg(C s H s )2 ~[M(CSHs)2J, (M=Ca, Sr)
5 o
CaC 2 C H ) [Ca (C H ) ]
ry
(in Jig. NH 3 ) 5 5 2
(G) Structure of biscyclopentadienylmagnesium, i.e. [Mg(Tl s-C sH s)2]: It has the staggered sand-
ra
wich structure of D Sd symmetry (ef structure of ferrocene). The bonding bears both the ionic and
covalent interaction.
ib
(H) Structure of [Ca(C SHS)2]: Ca is coordinated by four planar cyclopentadienyl rings which actu-
yl
ally act as the bridging ligands. Two of the rings coordinate as 115-C5H 5 giving the Ca-C distance 275
pm; one ring coordinates as 113-C5H 5 giving different Ca-C distances, i.e. 270 pm (1 distance), 279 pm
m
(2 distances), 295 pm (remaining 2 distances). These three polyhapto rings (i.e. two 115-C5H s and one
113-C5H 5) are approximately trigonally oriented around the Ca-centre. The fourth ring binds as a lll-
he
C 5H s ring (having the Ca-C distance 310 pm) which stands almost perpendicular to the trigonal plane
constituted by the three polyhapto rings. Thus, it is quite interesting to note that the Ca-centre
lc
simultaneously binds with two 11 5-, one 113- and one lll- cyclopentadienyl rings. Actual structure is
more complicated because of the bridging nature of the rings.
ea
th
e/
t.m
e
er
H
Fig. 9.15.3.3 Structural representation of [Ca(Cp).d unit in solid polylneric [Ca(Cp)2]' i.e. [Ca(Cph]x'
Note:· A, Band C - Cp rings trigonally coordinate Ca; 0 - Cp ring is approximately perpendicular to the trigonal plane
k
• Ca-C distance = 275 pIn for the If-Cp rings; Ca-C distance = 310 pm for the ll'-Cp ring; for the 113-Cp rings,
lic
all Ca-C distances are not equal

• C - Cp ring bridges another Ca2+ as a 115-Cp ring; B - Cp ring bridges another Ca:?+ as a ll'-Cp ring; 0 - Cp
C
ring bridges as a 115-Cp ring to another Ca2 •
(I) Bis(cyclopentadienyl)beryllium: It can be easily prepared in the following metathesis reaction.

BeC1 2 + 2Na[C sHs] ~ [Be(C sH s)2] + 2NaCl.
The structural features of [Be(C sH s)2] are quite interesting. In gas pas, it exists as [Be(lls-C sH s)2]
which is an anti symmetrical sandwich while in solid state it exists as [Be(11I-CsHs)(lls-CsH:J], i.e. one
ring binds as 11 s while the other ring binds as 11 1• It leads to 8e in the valence shell (c.f. octet rule). The
same octet rule is maintained in [Be(1l5-C sH s )X] (X = H, CI, Br, etc.).
If [Be(C sHs)2] is supposel} to have the ferrocene type structure, i.e. [Be(Tl s-C sH s)2] then it
requires to accommodate 12e in the valence shell of Be. But it is not possible.
~I Be
154 pm
,
,'194 pm
ry
X
[Be(Tl 5-Cp)X]
ra
[Be(Tl 1-Cp)(Tl 5-Cp)]
ib
Fig. 9.15.3.4 Structures of [Be(n5-Cp)X] and [Be(n1-Cp)(n5-Cp)].
yl
It indicates that the structural features of [Be(Cp)2], [Mg(Cp)2] and [Ca(Cp)2] are different from
m
those of ferrocene.
9.15.4 Structure and Properties of the Organometallics of Group 13 Elements
he
(A) Synthesis: The alkyl or aryl compounds are readily prepared by using either the Grignard reagent
or lithium alkyls which are allowed to react with the trihalides of Gr. 13 elements.
lc
BF3 + 3RMgX ~ BR 3 + 3Mg 2+ + 3F- + 3X-
ea
BF3 + 3LiR ~ BR 3 + 3LiF
GaCl 3 + 3LiR ~ GaR 3 + 3LiCI
th
AICl 3 + 3LiR ~ AIR 3 + 3LiCI

R may be an alkyl or aryl group.
e/
However, transmetallation may be used to prepare the said organometallics. In this process, in HgR 2,
mercury is replaced by a more electropositive metal.
t.m
3HgR 2 + 2M ~ 3Hg + 2MR 3, (M = Ga, AI).

AIR 3 is widely used as a polymerisation catalyst. Its industrial synthesis is carried out in the
following reaction.
e
2AI + 3H 2 + 6 RCH = CH 2 ~ 2AI(CH 2CH 2R)3,

Probably, the initially formed species AI-H adds to the C = C bond of the alkene.
er
(B) Structural features of MR3 (M = B, AI, Ga, In): The M-C bond strength runs as (cf Table
H
9.16.1.1): B-C) AI-C) Ga-C) In-C) TI-C. This group trend is also maintained for the Gr 12,
14 and 15 elements. For the heavier congeners, the bond strength decreases because of the longer bond
length.
k
BR) is monomeric; AIR 3 is generally dimeric (if not sterically disfavoured by the bulky R-groups);
lic
GaR 3 and InR 3 are monomeric.

In attaining the dinleric structure, it will use two 3c-2e M-C-M bridges. The size of M runs as:
C
B <Al < Ga < In. For BR 3, the bridged compound will experience a severe steric repulsion because of
the smaller size of boron and it will disfavour the dimeric structure. For the heavier congeners like
Ga, In, the large size will make the M-M distance too long to allow the sitting of the bridging 'C'
atom. Moreover, for the heavier congerers (i.e. Ga, In), the reduced bond energy (i.e. longer
M-C bond) does not favour the bridged structure with the electron deficient bridge bonds.
The bonding in Al 2R 6 has been widely discussed in Sec. 9.21, Vol. 2. In A12Me6' the methyl bridged
dimers consists of 3c-2e bonding giving rise to the AI-C~-AI bridge (cf. AI-C h ) AI-Cr, band t
denote the bridging and terminal groups). The involved orbitals in the 3c-2e bonding are:
one Sp3 orbital of the CH 3 group, one Sp3 orbital from each AI-centre.
These electron deficient AI-C~-AI bond is different from the AI-CI-AI bridge (i.e. chlorido-bridge
bond) consisting of 2c-2e bonds (i.e. 3c - 4e system). In making the bridge, each Cl-atom provides
two p-orbitals and three electrons; one AI-centre provides a vacant sp3-hybrid orbital while the other
AI-centre provides one sp3-hy;:rid orbital with an unpaired electron. This constitutes the 3c-4e bond-
ing system. The larger AI- CI- AI, bond angle (i.e. 90° vs. 75°) arises because the bridging halogen
ry
ra
3c-2e bridge
ib
e
yl
1\2)
m
he
AI - - - - . AI = 260 pm
lc
ea
th
e/
_ + Nodal plane
------0
t.m
e
er
AI AI
AI~
AI
() \2) ()
H
AI AI = 270 pm
(1l1-Ph perpendicular to the AICAIC plane)
k
lic
8
C
CI
!fCI~
AI AI
AI\j
@ \2)
H"I/
/AI ...........
,/ I H I
H~I/H"
AI AI
/
ry
I
H/ "'-H/ I""
ra
"'\/H
/\1"
ib
(e) (AIH 3)n
yl
Fig.9.15.4.1 Structural representation of some organometallics of aluminium and some related compounds in terms of
m
bonding.
he
provides 2 orbitals for the bridge formation while in the AI-CIl-AI bridge, the bridging C-centre
provides one orbital.
The bonding characteristic features of the bridging Ill_Ph (that lies perpendicular to the line joining
lc
the AI-centres) are quite interesting. In terms of the number of orbitals participating from the bridging
ea
group, the bridging phenyl group is similar to the bridging halogen. The carbon centre of the
bridging phenyl group provides one sp 2-hybrid orbital to produce the 3c - 2e AI-C-AI bond as
usual. In addition to this, the C-centre can provide a p1t-orbital for an interaction with the AI-orbitals.
th
More correctly, a 1t-HOMO of the bridging phenyl group donates the electron to the AI-orbitals. For the
alkyl bridging group, no such additional bonding is possible. In fact, the Ph-group can make a better
e/
bridge than the alkyl R-group. The bridging efficiency runs as:
t.m
bridging efficiency: R2P-) X- ) H- ) Ph- ) R-

The better bridging capacity of H- than that of R- arises from the fact that smaller 'H' can sit
better than the bulkier alkyl group between the metal atoms. The above sequence explains the fact that
in A1 2R4 Ph 2, instend of the alkyl group, the phenyl group acts as the bridging group. In B2H 2R4 and
e
A1 2H 2R4 , H not R makes the bridge bond. These are illustrated in the following examples.
er
H Ph
A A
H
R" /R R" /R
k
/AlyAI" /AlyAI"
R R R R
lic
H Ph
C
BPh 3 vs. AIPh 3 (Relative Lewis acid strength; see Ch. 14, Vol. 3)
Ph
'" _ _ Ph", A / P h
/ B~+
~-
_ Ph /y"
AI AI
Ph
(CsH s as a 1t-donor) Ph
The mechanism of scrambling of Me-groups in Al2Me6 has been discussed in Sec. 10.10. Here it
is worth mentioning that the tendency of dimerisation of AIR 3 decreases with the increase of bulkiness
ofR.
2AIR) ~AI2R6' (K decreases with the increase of the size of R).

In fact, for R = mesityl group, AIR 3 predominantly exists as a monomer.
ry
ra
ib
(Mesityl group, i.e. 2,4, S-trimethylphenyl)
yl
CH 3
m
Here it is interesting to note that though TIR 3 is known to exist as a monomer, but the linear species
[R-TI-R]+ (R = Me) also exists. In fact, it is isoelectronic and isostructural with R-Hg-R.
he
bridging efficiency: TIX 3 + 2RMgX ~ [TiR2]X + MgX 2.
(C) Carbnionic character in the M-C bond and protonolysis or protolysis of the M-R bond:
lc
Organometallics of the electropositive metals experience the polarisation in the M-C bond as
M8+-C8-. The more electropositive character of the metal generates the more carbanionic character
ea
on C.
Between the alkylaluminium and alkylboron compounds, the 'AI-C' bond is more polarised
th
than the 'B-C' bond. It is due to the more electropositive character of aluminiulTI.
For MR 3 (M =AI, Ga, In, TI), the carbanionic character in the M-C bond decreases as the electro-
e/
positive character of the metals decreases in the following sequence:

t.m
AI-C) Ga-C ) In-C) TI - C

Thus among the organometallics of Gr-13, the carbanionic character is maximum in the 'AI-C'
bond. This charbanionic character in the M-C bond leads to protolysis or protonolysis of the M-R
bond even by the very weak Bronsted acids like alcohol, water, etc. This is favoured maximimu in the
e
AI-R linkage among the organometallics of Gr13. Generally, H20 or R'OH makes a nucleophilic
er
attack on the metal centre having a vacant orbital. Then protolysis of the M-R bond occurs by the
coordinated nucleophile bearing a protonic hydrogen. But protolysis may also occur by the nucleophile
H
(e.g. H 20, R'OH) before attacking the metal centre. Both the protolysis and nucleophilic attack may
occur in a concerted process as in BR 3 . Success of the overall process rests on the push-pull mecha-
k
nism. Nucleophilic attack gives the push while protolysis gives the pull.
lic
~/R'
-
C
R'OH
Associative path:
:UII@~ 2
R M(OR')+RH
(Push-Pull effect)
(R' = H or alkyl group)
The primary isotope effect suggests that the 'O-H' bond breaking leading to protolysis of the
M-R bond is making a significant contribution. The process is so favoured for AIR 3 (compared to
other MR 3 of Gr. 13 elements) that most of the alkylaluminium compounds catch fire explosively in
water or alcohols. However, the reaction is slowed significantly with the stertically hindered alcohols
like tertiary butyl alcohol.
The above reactivity of R3M is a convenient route for the metal-alkoxide bond synthesis. If amines
(Le. R~NH or R'NH 2) are used in place of R'OH, then the above reaction leads to metal amides.
The reactivity of MR3 towards H 20, R'OH, R'NH 2 or R~NH follows the sequence:
AIR 3 ) GaR 3 ) InR 3 ) TIR3. «(f effect of M-C bond polarisation)
ry
The reactivity sequence is determined by the carbanionic character on the M-C bond. Let us
consider the hydrolytic products of AIMe3 and GaMe3.
ra
AIMe3 + 3H 20 ~ AI(OH)3 + 3CH4
ib
nGaMe3 + nH 20 ~ [Me2Ga(OH)]" + nCH4
(n = 2, 3, 4)
yl
2GaMe3 + 2ROH ~ [Me2Ga(OR)]2 + 2CH4
m
R
he
Me"" /0", /Me
Ga Ga
Me
/""'-/""'-
0 Me
lc
ea
R
th
Thus AIMe3 undergoes a complete hydrolysis while GaMe3 experiences an incomplete hydrolysis.
'GaR 2' moiety is quite resistant to protolysis.
e/
It is due to the fact that the carbanionic character in the Ga-Me bond is relatively less compared to
that in the AI-C bond. GaMe2 moiety can be stabilised in [GaMe2(en)J+.
t.m
(D) Hydrolysis of DR3: The concepts of protolysis and push-pull effect explain why BR3 is inert in
the hydrolytic reactions. In fact, solvolysis of BR3 occurs in presence of a carboxylic acid. Mineral acid
is not efficient to catalyse the process. Because R'C02H can act as a nucleophile as well as a proton
e
donor to the leaving R-group.

er
H
#,0 A B-----A
2 \
R'-C~
I
l II r-!
P li)~'j
I U
PI
k
"OH U 0 H L
A3 B ~
~
lic
(Associative path) L
C--O
/
C
A'
(Push-pull effect)
The above reaction indicates the importance of both the protolysis of the B-R bond and nucle-
ophilic attack on the B-centre bearing a vacant orbital. It supports the push-pull mechanism. H 20 can
attack as a nucleophile but it is not efficient in carrying out the protolysis because of its weak acidic
character. Mineral acids can do the protolysis but they cannot provide the nucleophilic attack. R'C0 2H
can perform both the tasks to provide the push-pull effect.
Hydroperoxide (-OOH) can catalyse the hydrolysis of BR3 in the following mechanistic path which
also illustrates the importance of push-pull force.
-OOH H2 0
R3 8 .. R2 8 - R -----. R 8 - - - . R .~
-----I . R2 80H + ROH + OH
(Associative \. ) 2 ~i
path) .J 1
-0-0 0--0
V\
'" H
H
ry
(Push-pull effect)
It is evident that -OH cannot catalyse the process. Hydrolytic products, i.e. RB(OH)2 called boronic
ra
acid, may be obtained as follows.
ib
BEt3~EtB(OEt)2 +2H 20 ) EtB(OH)2 +2EtOH
(E) Lewis acidity: The MR 3 species of Gr. 13 are the electron deficient compounds whether they
yl
remain as the monomers or dimers. In the dimeric species of aluminium, i.e. A1 2R6, the electron
m
deficient 3c - 2e AI-CIl-AI bridge bonds are broken down to give the monomeric tetrahedral species
AIR 3(B) in presence of the Lewis base (B). In the adduct, all the bonds are the 2c - 2e bonds.
he
In general, the trialkyl and triaryl borons are the weak Lewis acids. These are weaker Lewis acids
than the boron trihalides or BH3, i.e. B2H6- Probably, steric effects, hyperconjugation, 1t-bonding,
lc
electron pushing inductive effect, etc. are the important factors to be considered. Steric factors in BR3
and BPh3 will disfavour the adduct formation. Electron pushing inductive effect of the Me-groups will
ea
reduce the Lewis acidity. In BMe3' hyperconjugation effect may further weaken the Lewis acidity
H
th
/
B-C-H
e/
"'H
t.m
In BPh3, the electron pushing mesomeric factor is important to reduce its Lewis acidity.
e
er
H
k
In fact, this electron pushing mesomeric effect in BPh 3 is more important than the hyperconjugation
lic
effect present in BMe3. It explains the Lewis acidity order:

BMe3 ) BPh 3
C
However, Lewis acidity of BPh 3 is well illustrated in the following reaction.

BPh 3 + LiPh ~ Li+[BPh4 ]-
The strong base Ph- is transferred from the weaker acid Li+ to the stronger acid B(III).
The anion BPh 4-, i.e. tetraphenylborate ion, is quite stable. This large anion is used to crystallise the
large cations in synthesis.
Lewis acidity of Al2Me6 is illustrated in the following reaction.
Al2Me6 + 2NEt 3 ~ 2Me3AI·NEt3
At the cost of the electron deficient 3c - 2e AI-CJl-AI bonds, the strong 2c- 2e bonds are
produced.
(F) ~-Hydrogen elimination: If in the metal-alkyl bond, there is a hydrogen in the ~-position, then
the ~-hydrogen elimination leads to the M-H bond and release of an alken~.
ry
Reverse of this reaction gives the addition of the M-H bond to an a~kene.
ra
When AIEt) is heated, it gives AIEt 2H and C 2H4 • AIEt 2H may remain as a dimer by using the
H-bridge. It is illustrated for triisobutylaluminium. ;')
ib
~(i-C4H9)2AI(H)AI(i-C4H9)2 +2H3C~C-CH3
yl
2AI(i-C 4H9 )3
H .~ H
m
CH 2
he
lc
ea
th
The AI-H~-AI bridge is more efficient than the AI-C~-AI bridg~.

e/
(G) AIR3 as a polymerisation catalyst: AIR 3 can catalyse the polymeris~tion of alkenes. It occurs
through the insertion of alkenes in the AI-C bonds.
t.m
(C 2H 4 ) Et
C 2H4 / Y
AI(C 2H s )3 ) Et(C2H4t-AI,\
(C 2H 4 )zEt
e
er
Al (CH 2CH 2R)3 ~AI(OCH2CH2R)3 2

H 0) Al (OH)3 + 3RCH 2CH 20H
H
For polymerisation of ethylene, the unbranched C-chain may contain upto 200 C-atoms. The polym-
erisation process, i.e. insertion of C 2H4 olefin in the AI-C bond occurs as follows.
k
lic
C
~
'"
- A I - (C2H4)2Et
/
Note: Details of the polymerisation process and Ziegler Natta Catalyst have been discussed later.
(H) Organometallics of In(I) and TI(I): Due to the inert pair effect, + 1 state becomes stable
for the heavier congeners. In fact, In(I) and TI(I) have been stabilised in organometallics, e.g.
[TI(lls-CsHs)], [In(lls-CsHs)]. They exist as monomers having the pentagonal pyramidal geometry (C sv
symmetry). However, in solid state, they may remain in an associated condition. [TI(llS-CsH s)] is
prepared as follows:
TI(OH) + CSH6 (cyclopentadiene) ~ [TI(lls-CsH s)] + H2 0
ry
In the solid state, In(I) and TI(I) give the zig-zag chain in their polymeric forms, [M(lls-CsHs)]n, (M
= In, TI).
ra
'" /M", /M",
ib
c~ /c p c~ /c p
yl
M M
m
Cyclopentadienylthallium, i.e. [TI(Tls-CsHs)] is an important reagent used in synthesis. It has
some advantages over the alternative reagent NaCsH s which is highly reducing. Moreover, TICI pro-
he
duced as a product can be easily separated because of its insolubility.
Ga(III) gives [Ga(1l1-C sHs)3] having a trigonal planar structure, i.e.
lc
(11 1-CP)
ea
(r{..cp)-Ga/
"(11 -CP)
1
th
9.15.5 Structures and Properties of the Organometallics of Gr. 14 Elements

e/
(A) Synthesis: The halides MX4 are allowed to react with LiR or AIR 3 or RMgX (i.e. Grignard reagent).
t.m
SiCl4 + 4LiR ~ SiR4 + 4LiCI

3SnCl4 + 4AIR 3 ~ 3SnR4 + 4AICl3
SnX4 + 4RMgX ~ SnR4 + 4MgX 2
R nSiX4 - nare industrially very much important. They are prepared directly from the elemental silicon.
e
R SiX
er
Si+RX 300-500°C )
Cu-Catalyst 0 4-0
H
Si + MeCI ~ Me 2SiCl 2 + MeSiCl 3 + Me 3SiCI

{ca. 70%) {ca. 15%) {ca. 5%)
Such chlorosilanes are used in the manufacture of silicone polymers.
k
Tetraethyl lead is commercially important because of its use as an antiknock compound. It is

lic
prepared as follows:
4C 2HsCI + Pb + 4Na ~ Pb(C 2Hs)4 + 4NaCl.
C
Without sodium, an endothermic reaction produces PbEt4 but in presence of sodium, the overall reaction
becomes exothermic. This is why, instead of pure lead, Pb-Na alloy is used.
4C 2HsCI (1) + 2Pb(s) ~ Pb(C 2Hs)4 (I) + PbCl 4 (1), ~Ho = +286 kJ
PbCl4 (1) + 4Na(s) ~ Pb(s) + 4NaCI(s), ~Ho = -1331 kJ
4C 2HsCI (1) + Pb(s) + 4Na(s) ~ Pb(C 2l-!S)4 + 4NaCI (s), ~Ho = -1045 kJ
Pb(C 2Hs)4 can also be prepared in the following route
disproportiooatioo
) Pb + PbR4
(B) Less carbanionic character in the M-C bond and resistance to solvolysis through the
associative path: Si, Ge, Sn, Pb are the heavier congeners of carbon. Consequently, electronegativity
difference is not significant to polarise the M-C bond significantly. Thus, protolysis of the M-R
bond for the Gr. 14 elements is a relatively difficult task compared to that for the M-R bonds of
the Gr. 13 elements. In Si, Ge, Sn, Pb, there are vacant d-orbitals to accommodate the nucleophilic
attack by H20 but the starting compound MR4 is already sterically crowded. Consequently the nucleo-
ry
philic attack to increase the coordination number through the associative path is sterically disfavoured.
Thus the two factors: (i) poor tendency of the M-R bond to undergo protolysis due to the reduced
ra
carbanionic character in R, (ii) unfavour to accommodate the nucleophilic attack (associative path)
due to steric crowding, make the organometallics MR4 of Gr 14 element more resistant to hydroly-
ib
sis compared to those of MR3 of Gr 13 elements. It explains why the AI-CH 3 bond is unstable but the
yl
Si-CH 3 bond is stable with respect to the hydrolysis reaction.
(C) Siloxanes: These compounds are characterised by the presence of Si-O bond. The Si-C bond
m
is resistant to protolysis but the Si-X bond can undergo protonation easily (ef electronegativity difference
between Si and C; and between Si and halogen).
he
Me 3S1· - CI H 20
-Hel)
Me S'1 (OH)
3
dimerisation
)
Me S·1 -
3
0 ~
S·M
1 e 3
lc polymerisation
) polymer product
ea
(both linear and cyclic)
th
Me" /Me
/Si,
o a
e/
Me.. . . . . !i s!/Me
t.m
Me/ '0/ ~Me

(linear polymer) (cyclic polymer)
HO[Si(CH 3 )2 0 ]x H (Me 2 SiO)3
e
er
Me,
O--Si- Me
H
Me, / \
Me/r tMe
k
lic
o Si
\ /~e
C
.--Si--O
Me \
Me
(cyclic polymer)
(Me 2SiO)4
Hydrolysis of MeSiCl 3 produces a cross-linked polymer commonly known as silicones which are
industrially very much important. The silicones have been discussed separately in Sec. 1.12.
(D) Silazenes: Ammonolysis of chlorosilanes, i.e. protolysis of the Si-CI bond by the H-N bond
(present in NH 3, RNH 2 and R2NH) and nucleophilic attack by N on Si produces a variety of compounds
characterised by the Si-N bond.
Me 2 SiCl 2 _N_H3~) ~Me2SiNH)3 + (Me 2SiNH)4,

cyclic polymers
ry
3
HSi(CH 3)2 Cl NH )(Me 2 (H)Si)3 N
ra
All the N-H bonds of NH 3 may not participate for protolysis of the Si-CI bond. All the three
N-H bonds participate for protolysis of the less hindered chlorosilane like HSi(Me)2Cl.
ib
(E) Organosilicons with catenation: The Si-Si bond is relatively weaker than the C-C and
C-Si bonds.
yl
Bond energy (kJ mol-I): C-C (348» C-Si (318) > Si-Si (226). This is why, the Si-Si catena-
m
tion is noted in some limited cases. The corresponding organosilicones are:
R 3Si-SiR3, R 3Si-SiR2-SiR 3, (SiR 2)4 (cyclic) (R = Me).
he
) Si = Si ( and ) Si = C ( bonds can be kinetically protected from their polymerisation by using
lc
the bulky substituents like mesityl group, i.e. 2, 4, 6-trimethylphenyl group, xylyl group, i.e. 2, 6-
ea
dimethylphenyl.
th
e/
t.m
e
er
H
In fact, the 3p1t-3p1t overlap in the Si=Si double bond is quite inefficient because of the elongated
k
Si-Si distance in the a-skeleton (see Chapter 10, Vol. 2). It makes the Si=Si double bond relatively
lic
unstable (cf. Si=Si bond 216 pm while Si-Si bond 235 pm; C=C bond 134 pm and C-C bond 154
pm). This is why, the Si=Si or Si=C bonds tend to adopt the structure having the single bonds.
C
It is attained through the polymerisation. This polymerisation can be prevented by using the bulky
R-groups.
In disilenes (Le. )Si = Si() the energy separation between the HOMO (1t-BMO) and LUMO
(n*-ABMO) is 3 eV (= 400 nm) while in the alkenes the corresponding energy separation is 6 eV(= 200
nm). This is why, disilenes are more polarisable, i. e. softer and they absorb light in the visible or near
UV region. Thus they are coloured while the alkenes are colourless absorbing the light in the UV-
region. The HOMO of disilenes is of higher energy than that of alkene while the LUMO of disilene is
of lower energy than that of alkene (see Fig. 14.7.5.8, Vol. 3). It makes disilene a better Lewis base
(electron pair of HOMO is to be donated) and it is also a better Lewis 1t-acid (electron is to be
accepted in the 1t*-LUMO).
(F) Organometallic compounds of Ge, Sn and Pb: Because of the inert pair effect, they can form
the organometallics in +2 oxidation state also. Thus, they have the organometallic compounds in both
+2 and +4 oxidation states while silicon forms the organometallics in +4 oxidation state only. Obvi-
ously, for the heavier congeners, +2 state is more stable. It explains the stability order: SnR2 ) GeR2. The
M-C bond energy runs in the sequence (el Table 9.16.1.1):
Ge-C ) Sn-C ) Pb-C (ef. periodic trend of covalent radii)
ry
This is why, PbEt4 easily experiences the thermal dissociation releasing the ethyl radical.
ra
PbEt 4 ~Pb+4.Et
This easy thermal decomposition allows PbEt4 to be used as an antiknock compound in gasoline.
ib
In fact, the released ethyl radical acts as a radical scavanger, i.e. radical chain terminator. This
yl
prevents the explosive combustion of gasoline (see the author's book, Environmental Chemistry with
Green Chemistry).
m
The chemistry of organogermenium is very similar to that of silicon but the Ge-C bond is less
he
stable than the Si-C bond. GeR4 and RnGeX4- n are more resistant to hydrolysis. The character of
hydrogen is different in the following pair of compounds, Ph 3Si-H and Ph 3Ge-H.
Ph 3Si-H + LiR ~ LiH + Ph 3Si-R. lc
(hydridic character giving rise to metathesis)
ea
Ph 3Ge-H + LiR ~ RH + Ph 3Ge-Li
(protonic character giving rise to metallation)
th
Now the catenated compounds like R 2Ge=CR 2 (germenes), R 2Sn=CR 2 (stannenes),

R2Ge = GeR2 (digermenes), R 2Sn = SnR2 (distannenes) have been characterised for the bulky R-
e/
groups (e.g. mesityl, xylyl) which can prevent polymerisation. This aspect has been discussed in
connection with the stability of disilenes. It is interesting to note that in contrast to oletins, digermenes
t.m
and distannenes are nonplanar. In )C=C(, the Sp 2_Sp 2 overlap gives the a-bond and P1t - P1t overlap
gives the 1t-bond. On the other hand, in )Ge = Ge( or )Sn = Sn(, the sp2_p overlap occurs to give the
double bond. This nonconventional overlap between the Sp2_ a orbital and p-1t orbital is believed to
e
be responsible for the nonplanar structure and weak bent double bond.
er
p~~~~
H
R
M~~~
k
R~l~· ~
lic
++ ~p
C
+--
R 2
sp
(M = Ge or Sn)
(sp2-1one pair donated into the vacant p-orbital of the adjacent M-centre)
The above mentioned nonconventional bonding explains why the such multiple bonds are weak.
(G) Cyclopentadienyl complexes of Ge, Sn and Pb: The examples are:
[Ge(l1S-CsHs)] +, [Ge(l1s-CsHs)CI], [Ge(l1 s- CsHs)2], [Sn(l1 s- CsHs)2], [Pb(l1 s-CsHs)2]
All are in +2 oxidation state. The structures are shown in Fig. 9.15.5.1.
ry
ra
ib
/
yl
--Pb
m
o
~
he
.....---Pb
lc
ea
th
[M(1l5-Cp)2]
Pb-
M = Ge, Sn
/
e/
t.m
Fig. 9.15.5.1 Cyclopentadienyl complexes of Ge(II), Sn(II) and Pb(II).
In gas phase, [M(llS-C sH s)2] (M = Ge, Sn) is angular with a stereochemically active lone
pair. Similarly, [Ge(llS-CsHs)(CI)] is also angular with a stereochemically active lone pair.
[Ge(lls- CsHs)]+ also bears a stereochemically active lone pair. In solid state of [Pb(lls-C sHs)2], one
e
CsH s ring is placed perpendicular to the Pb--Pb line and the other ring is only linked to only one
er
Pb-centre. The lone pair of Pb participates in linking the chains through the interaction with a neigh-
bouring chain CsHs-ring. In contrast, [Pb(lls-CsMes)2] is monomeric.
H
(H) Organotin Compounds: These are important for their industrial uses such as:
(i) [R 2SnX 2] (R = n-octyl, X = laurate, maleate) are widely used as the stabilisers for the PVC
k
plastics against discolouring and becoming brittle. They protect PVC by preventing the dehydro-
lic
chlorination through the exchange ofreactive chlorine by their X-groups. Then can also scavange
HCI which is produced. The released HCI can degrade PVC rapidly. R2SnX 2 can act as an anti-
C
oxidant and thus it protects PVC from the degradation by the attack of atmospheric O 2. In fact,
this is the largest use (about 75%) of organotin.
(ii) Organotin compounds like BU3Sn(OH), Ph 3Sn(OAc), etc. are also used as the agricultural pes-
ticides to control fungi, bacteria and insects.
(iii) [0(SnBu3D)2] is used as a wood preservative. This is also used as the antifouling agents in the
paints for hulls of boats and marine vessels.
However, there are some objections against the use of organotin compounds as the biocides. For
example, 0(SnBu3)2 kills not only barnacles but also oysters and many other harmless marine
organisms (see the author's book, Environmental Chemistry with Green Chemistry).
(iv) Bu~SnX2 (X- = acetate, laurate, etc.) is used as a catalyst in the manufacture of polyurethanes
and as a curing agent for silicones.
(v) Organotin compounds are also finding uses as the useful reagents in organic synthesis.
Organotin compounds may be prepared as follows:
SnX4 + 4RMgCl ~ SnR4 + 2MgCl 2 + 2MgX 2
Sn + 2RX ~ R2SnX2 (Rochow synthesis).
ry
RnSnX4- n are generally prepared by the scrambling reaction between SnX4 and SnR4.
ra
SnX4 + SnR4 ~ 2R2SnX2; SllX4 +SnR4 ~ R3SnX + RSnX 3
Here it may be mentioned that the compounds like R 2SnX 2, R 3SnX, etc. are generally in associated
ib
forms via the bridging X-groups. The polymeric structure of Me3SnF and Me2SnCl2 are well known
(Ch. 10, Vol. 2).
yl
9.15.6 Organometallics of the Gr 15 Elements
m
Among the Gr. 15 elements, Nand P are nonmetals. Thus the organic compounds of As, Sb and Sn
he
belong to this group. The M-C bond strength runs as: As-C) Sb-C ) Bi-C (cf Table 9.16.1.1).
High electronegativity of arsenic introduces (cf. secondary periodicity, Vol. 1) a weak carbanionic
character in the As-C bond. lc
(A) Examples of organoarsenic(III and V) compounds: Some representative examples are given
ea
below.
th
e/
<Q(-ASPh 2
t.m
AS-<pJ
© As
00 As [Q( AsPh
e
o-phenylenebis(dimethylarsane) 2
(Arsabenzene) (1-Arsanaphthalene) (a chelating ligand) AsPh 2
er
tris-( o-diphenylarsinophenyl)arsane
(A bulky tetradentate ligand)
H
Me2AsO(OH) MeAsO(OH)2
Dimethylarsinic acid Methylarsonic acid
k
i.e. cacodylic acid

lic
R3 As = 0 Me2As-AsMe2 AsR/ (cf. NR 4+) AsPh 4 +

(Tetramethyldiarsane) (Tetraalkylarsonium) (Tetraphenylarsonium)
C
(B) Examples of organoantimony and organobismuth compounds: MMe3, MPh 3, MPhs, RSbX 2,
R2SbX, RSbO(OH)2 (stibonic acid), R 2SbO(OH) (stibinic acid), Me2SbX3, MR4+, MPh 4+, Sb~-.
(M = Sb, Bi)
9.15.7 Preparation and Properties of Organometallics of Gr 12 Elements

(A) Discovery of zinc alkyls i.e. ZnR 2 by Sir Edward Frankland in 1849 is a landmark in the
history of organometallic chemistry. Though, Zeise salt K[Pt(1l2-C:l!4)C1 3 ] (1831) and the dimer
[{Pt(1l2-e2H4)Cl(J.l-Cl) }2] (1827) were discovered earlier, the Frankland's discovery may be considered
as the real beginning of organometallic chemistry.
(B) Synthesis: The common routes are discussed below.

o
Zn + RX .. boiling ) ZnRX ~ ~ ZnR + ~ ZnX
(m mert atmosphere) 2 2 2 2
In fact, ZnR 2 distills off.

ZnR 2 may be obtained easily from the organomercury compound HgR 2, alkylaluminum, or
ry
alkyllithiurn.
HgR 2 + Zn --1 ZnR2 + Hg.
ra
ZnX 2 + Al 2R 6 --1 ZnR2 + (R 2AIX)2
G ZnX 2 + 2LiR --1 ZnR 2 + 2LiX
ib
MR2 can react wIth MX 2 to produce the Grignard type reagent. It is illustrated below.
yl
CdMe2 + CdI 2 --1 2MeCdI.
MR2 + MX 2 --1 2MRX
m
HgR2 can be obtained as follows:
he
HgCl 2 + 2LiR --1 HgR 2 + 2LiCl.
By using the Grignard reagent RMgX, MR2 can be obtained as follows:
MCl 2 + 2RMgX --1 MR 2 + 2MgXCI lc
RMCI + RMgX --1 MR 2 + MgXCI
ea
RHgX may be prepared as foHows:
HgX 2 + RH --1 RHgX + HX, (Mercuration)
th
2Hg + 2RX --1 HgR2 + HgX 2, HgX 2 + 2Na --1 Hg + 2NaX.

(C) Structure: In gaseous phase, MR2 (M = Zn, Cd, Hg) is linear. Existence of the monomeric
e/
species MR 2 indicates that these do not tend to have the alkyl bridges.
t.m
(D) Reactivity: In general, MR2 can act as the Lewis acids and the Lewis acid strength runs as:
ZnR2 ) CdR 2 ) HgR2
The carbanionic character in the M-C bond runs as:
e
Zn-C ) Cd-C) Hg-C (cf. electropositive character: Zn > Cd > Hg)

er
The better Lewis acid and carbanionic character (which favours the protolysis of the M-R bond)
support the ease of hydrolysis of MR2 in the following sequence:
H
ZnRi ) CdR 2 ) HgR2

In fact, ZnR 2, i.e. alkylzinc compounds are pyrophoric and are readily hydrolysed. ZnR 2 reacts
k
with air also. CdR 2 reacts very slowly while HgR2 is quite stable. The hydrolysis or alcoholosis of MR2
lic
can be represented as follows.
RM---a
C
PULL
RM--R
o\.~
~it~
Push-pull p
~ RM-OR'+RH
.step
O--H
(M = Zn, Cd)
!
• /U • 0- - - - - - - - - . H
R'
R
,/
MR 2 can react with NH 3 in the same way. In this regard, ZnR2 or CdR2 is similar to LiR or RMgX.
ZnR 2 being a relatively stronger Lewis acid can form an adduct with the chelating agent like bpy.
Me", /N
o
ZnMe2+bpy~ i. e. [Zn(bpy)Me21
/zn"
Me NO
ry
ra
Lewis acidity of ZnR 2 is also evidenced from the formation of the species like [Zn(C 2Hs)3]-'
[Zn(CH 3)4]2- in the reaction with suitable alkyls of alkali metals (MR).
ib
ZnR 2 ~ ZnR 3' ZnR~-
yl
Similarly, the Lewis acidity of CdMe2 is evidenced by the presence of [Cd(bpy)Me2]' [CdMe2(pY)2l
m
Here it is important to point out that in ZnR 2 or CdR b 14 electron configuration (10 + 2 x 2) is attained
while in [M(bpy)R 2] (M = Zn, Cd), 18 electron configuration (10 + 2 x 4) is attained. It has been found
he
that [M(bpy)Me2] is more stable than MMe2 (M = Zn or Cd). It supports the importance of 18e rule
in relation to the stability of organometallics. It may be mentioned that [CdMe2(py)] (16e configuration)
is less stable than [Cd(bpy)Me2] (18e configuration). lc
ea
Among M(Me)2 (M = Zn, Cd, Hg), only ZnMe2 can add to the carbonyl bond.
CH 3
th
&- 0+ I
+ H3C-ZnCH 3 ~ R2C-O-ZnCH 3
e/
t.m
Polarisation in the Cd-C or Hg-C bond is so small that HgMe2 and ZnMe2 cannot add to the
carbonyl group. In the Reformatsky reaction, probably an organozinc intermediate is produced.
e
er
H
CdR2 which is less reactive than ZnR2 can be used to prepare the ketones from the acid chlorides.
2RCOCI + CdR~~ 2RCOR' + CdCl 2
k
It may be mentioned that in this reaction, RMgX cannot used because RMgX further reacts with the
lic
ketones produced.
(E) Reactivity of the organomercury compounds: HgR2 is widely used to prepare the organometallics
C
of more electropositive metals by interchange, i.e. transmetallation.
HgR 2 (transmet+:1'»
atlon
MR n + Hg ; (M =alkali metals, alkaline earth metals, Zn, AI, Ga, Sn, Pb, etc.)
Organomercury compounds of the type RHgX are well known. For X- = Cl-, Br-, 1-, CN-, OH-, they
are covalent and linear molecules like R-Hg-X. Such covalent compounds are water insoluble but
soluble in organic solvents. But, for X- = N0 3-, P- or 1/2501-, they are ionic and water soluble. Many
RHgX derivatives, e.g. C 6H sHg(OAc) i.e. PMA called phenyl mercuric acetate, are used as the
pesticides. But because of the toxicity of mercury, their use is being restricted. RHgX can be easily
prepared from R-H through mecuration (meaning Hg-C bond formation).
Stability of HgR 2 : thermodynamic stability VB. kinetic stability

Remarkable kinetically stability of HgR2 arises for the following reasons.
(i) Very poor Lewis acidity disfavours the nucleophilic attack on Hg(II) (cf. Hg(II) is highly
reluctant to lose its linear structure by accommodating a nucleophile; see Chapter 4). (ii) Very low
polarity in the Hg-C bond (i.e. very poor carbanionic character) disfavours both the electrophilic
ry
attack on carbon and nucleophilic attack on mercury. (iii) Poor carbanionic character prevents
the protolysis of the Hg-R bond and consequently R becomes a very poor leaving group. (iv)
ra
Hg-O bond is weaker than Hg-C bond (cf HSAB principle) and thus hydrolysis is
thermodynamically disfavoured.
ib
For the nucleophilic substitution in the Hg-R bond, the push-pull mechanism through the
yl
nucleophilic attack on Hg(II) and protolysis of the Hg-R bond appears to be kinetically
unfavourable.
m
ZnR2 is pyrophoric while HgR 2is quite stable in air. Because of the tremendous kinetic stability
of the Hg-C bond, Hg-CH3+ cation can survive throughout the food chain to create the hazard
he
(cf Minamata disease).
Here, it is worth mentioning that the Hg-C bond is not thermodynamically very much stable
lc
(cf -120 kJ mol- l bond energy) and in fact, the organomercury compounds are thermally and
photochemically unstable. Because of this inherent thermodynamic weakness in the Hg-C
ea
bond (cf periodic trend of size and M - C bond length), HgR 2 can be widely used to prepare the
organometallics of more electropositive metals by transmetallation.
th
R-H + HgX 2 ~ R-HgX + XH, (R = alkyl and aryl group).

e/
C6H6 + Hg(OAc)2 ~ C6HsHg(OAc) (PMA) + AcOH.

t.m
e
Addition of HgX 2 to an olefinic double bond is also an example of mercuration.

er
HgX 2 ) R C CR
H
(mercuration) 2 - 2
I I
k
X HgX
(cr -bonded complex)
lic
The above reaction product bears both the Hg-C and C-O bonds and the above reaction is de-
C
scribed as oxomercuration. Acidification of the oxomercuration product can regenerate the starting
olefin.
R2C-CR2+HCI~R2C=CR2 +R'OH+HgXCI
I I
R'O HgX
Mercurochrome (merbromin) is a water soluble organo-mercury hydroxo compound (a derivative
of fluorescein) used as an antiseptic agent. But because of the toxicity of mercury, its use is being
restricted and in many countries, it is banned. Organomercury compounds generally restrict coordination
number to 2 but in some rare cases, the coordination number may be increased, e.g. [Hg(bpYJMe]+,
[HgCI(2-pyridylphenyl)] .
HgOH
Na+-o~o~o
)lA~~ H9-Cll
ry
Br C Br
~CO;Na+ I
ra
N
ib
(Mercurochrome)
yl
(F) Cyclopentadienyl compounds: Methyl(cyclopentadienyl)zinc(II) i.e. [Zn(lls-CsHs)Me] is
m
monomeric in gas phase but in solid state it exists in polymeric forms constituted by the zig-zag chains.
In the Zn-Zn segment, lls-CsHs is perpendicularly positioned at the mid point. Thus, each CsHs
he
ring is pentahapto with respect to two Zn-centres (cf the polymeric structure of [Pb(lls-Cp )2],
Fig. 9.15.5.1).
lc
[Hg(C sH s)2] is monomeric in gaseous phase but here the CsH s rings bind as 1l1_CsHs giving rise to
the Hg-C (J bonds. Thus it is [Hg(1l1_C sHs)2] which can explain both the ir and NMR spectra. But
ea
the structure, [Hg(llS-Cp )2] cannot explain the experimental findings (see Fig. 10.11.3.3a). Similarly,
[Hg(CsHs)X] is [Hg(lll-CsHs)X]. It indicates the reluctance in forming the metal-carbon 1t-bonds in
th
the cyclopentadienyl compounds of Hg(II). In terms of NMR data, the molecules are fluxional in nature
and all the 5C atoms of a CsHs ring appear indistinguishable. This phenomenon is described as ring
e/
whizzing. However, X-ray study on [{Hg(1l1-CsH4PPh 3)I2 }2] confirms the presence of the Hg---C a-bonds
for each ring in the dimer.
t.m
The structures of cyclopentadienyl complexes of Zn(II) and Hg(II) are shown in Fig. 9.15.7.1.
0L'-H9-----0
H Ph 3 P V ~H ......... 1........... ./1
~...................../
e
~ ~ I/H9~I H9~
er
w~
H
PPh 3
(a) Cyc10pentadienyl complexes of Hg(II). Note: Fluxional character, i.e. all the C-atoms are indistinguishable in NMR
k
time scale (i.e. Ring whizzing Phenomenon).

lic
CH 3
I CH 3
C
Zn I
%~zn~zn
(Gas phase)
I
CH 3
(Solid phase)
(b)
Fig. 9.15.7.1 (a) Fluxional cyclopentadienyl complexes of Hg(II). (b) Structure of [Zn(Tls-CsHs)Me] in gas and
solid phase.
9.16 SIGMA BONDED ORGANOMETALLICS OFTRANSITION METALS: METAL

ALKYLS, ARYLS, CARBENES AND CARBYNES
M-R M-Ar M=CR2 M == CR
Alkyl Complex Aryl Complex Carbene Complex Carbyne Complex
ry
9.16.1 Stability of the Sigma Bonded Alkyl and Aryl Compounds of the Transition Metals:
Thermodynamic Stability vs Kinetic Stability: Reactions of the Compounds
ra
For the main group elements, the a-bonded alkyl and aryl compounds are well known but for the
transition metals, such compounds are relatively less stable. Now the question arises whether the
ib
instability arises from the thermodynamic or kinetic factors. To answer the question, we should
yl
compare the M-C bond energy for the transition and main group elements.
m
Table 9.16.1.1 M-C Sigma Bond Dissociation Enthalpy (kJ mol-I)
he
(a) For the transition metals
[Ti(CH2CMe3)4] (198) [Mn(CO)5Me] (188) [WMe6] (160) [ZnMe2] ( 177)
[Zr(CH2CMe3)4] (250)
[Hf(CH2CMe3)4] (265)
[Re(COhMe] (220) lc [CdMe2] (140)
[HgMe2] (120)
ea
(b) For the main group elements
[A1Me3] (274) [SiMe4] (311) [AsMe3] (229)
th
[GaMe3] (247) [GeMe4] (249) [SbMe3] (214)

e/
[lnMe3] ( 160) [SnMe4] (217) [BiMe3] (141)

[PbMe4] (152)
t.m
(Note: For the main group elements, the M-C bond energy decreases for the heavier congeners
in a Group while the trend is opposite for the transition elements.)
From Table 9.16.1.1, it is evident that if the main group elements can form the stable M-C sigma
e
bonds then in terms of bond energy, the transition metals are reasonably expected to form the stable
er
M-C sigma bonds. Thus it indicates that the instability of the a-bonded organometrallics of the
transition metals is due to the kinetic factors.
H
In fact, for the such organometallics of transition metals, there are many low activation energy
requiring pathways for their decomposition. Such reaction pathways leading to the destruction of the
k
a-bonded alkyl or aryl compounds of transition metals are:

lic
• f3-hydrogen transfer-alkene elimination

C
• a-hydrogen transfer
• reductive elimination
• alkane elimination
• binuclear elimination
If the above reaction pathways causing the destruction of a-bonded organometallics of the transition
metals can be kinetically prevented, then stability of such organometallics will be achieved. These
aspects are discussed below.
A. p-hydrogen-alkene elimination reaction: When the metal centre is coordinatively unsaturated, this
path easily destroyes the compound. This is illustrated below.
~Lnl-l - L
n MH+C2 H4
ry
II III
ra
It is evident that for the above reaction to occur, it requires one vacant coordination state for the
formation of the transition state. If the vacant coordination site is available then it can occur without any
ib
difficulty. If such a vacant coordination site is not available then dissociation of a ligand can provide the
required coordination site. The above reaction can be prevented in the following ways.
yl
(i) The 1t-bonding ligands like CO, l1s-CsHs, PR 3 etc. can firmly block the coordination sites to
m
prevent the B-hydrogen transfer. Such strongly 1t-bonded ligands cannot be easily dissociated
to provide the required vacant coordination site. Examples of such complexes are: [TiCI3Me3],
he
[Ti(bpy)Me4], [Mn(CO)sR], [Fe(CO)2(l1 s- CsHs)Me], [Cd(bpy)Me2]
(ii) For the kinetically inert metal centres like Cr(III), Co(III), Rh(III), etc., coordination site cannot
lc
be easily vacated by the dissociation of a ligand and consequently the B-hydrogen transfer process
gets disfavoured. Moreover, for the such kinetically inert centres, increase of the coordination
ea
number in attaining the transition state is not possible. In summary, both bond breaking and bond
formation at the inert centre are kinetically disfavoured. This prediction is supported by the
th
stability of [Rh(C 2H s)(NH 3)s]2+ which is coordinatively saturated and the Rh lII - NH 3 bond is
kinetically inert towards substitution.
e/
(iii) For the alkyl groups lacking in B-hydrogen, the said B-hydrogen transfer process does not arise.
In fact, the M-C bonds using the groups like -CH 2Ph, -CH2SiMe3, -CH2CMe3' I-norbomyl,
t.m
etc. lacking in B-hydrogen are quite stable. This is why, [M(CH2CMe3)4] is more stable than
[M(C 2H s)4] (M = Ti, Zr and Hf).
B. a-Hydrogen transfer leading to decomposition: The CH 3 group lacks in B-hydrogen, but many
e
Me-group containing compounds like [TiMe4], [MMe6] (M = Re, W) are not stable. They undergo
er
decomposition.
n[WMe6] -7 3nCH4 + [{W(CH 2)3}n]
H
The reaction probably passes through a 4-centre transition state giving rise to the a-hydrogen transfer.
k
C-----C----
H3.
H
lic
I
I I
~
: : ~ W====CH 2 +CH 4
C
I I
• I
W - - - - - - - - - . CH 2
Decomposition of [Ta(CH 2Ph)s] occurs through the a-hydrogen transfer pathway. [Ti(CH 2CH 3)4] is
less stable than [Ti(CH 3)4] which can experience only the a-H transfer. It indicates that the {J-hydrogen
transfer is more easy to occur kinetically than the a-hydrogen transfer, if the required vacant
coordination site is available for the {J-hydrogen transfer path.
The factors which disfavour the stability of the M = C (carbene type compound) system will
disfavour the a-hydrogen transfer path. The factors favouring the stability of the carbene complexes
have been discussed in Sec. 10.3.
Note: The above reaction leading to destruction of [M(CH 3)x] may also occur through the homolytic
cleavage of the M-C bond giving rise to the CH 3 radical which subsquently abstracts a hydrogen atom
from the coordinated CH 3 group.
C. Reductive elimination leading to the destruction of the alkyUaryl complexes: The process can be
simply represented as follows:
(n+2)+
ry
LxM-R'~ LxMn++R-R'
I (R, R'= organic group or H)
ra
R
Some examples are:
ib
cis-[Pt(Ph)2(PPh3)2J~[Pt(PPh3)2J + Ph-Ph
yl
(biphenyl)
m
[ Au(Me)3 (PPh3)]~[Au(Me)(PPh 3)] + Me-Me
he
The groups to be eliminated must be in the adjacent positions.
L Et
)AU( ~Et-Me+[Au(Me)L] lc
ea
Me Me or
Me-Me + [Au(Et)L] L = ~Ph3
L\. Me
th
/AU( ~Me-Et+[Au(Me)L]
e/
Me Et
Decomposition of the alkyl hydrides may also occur through the reductive elimination process if the
t.m
Rand H groups are at the adjacent positions. It leads to alkane elimination. It is illustrated below.
e
er
The ease of reductive elimination of different organic groups as RH from [PtH(Phh 3)2(R)] follows
the sequence.
H
R: C6Hs)C2Hs)CH3)CH2CH===CH2
k
Here it is interesting to note that for the phenyl group, both the a- and {3-hydrogen transfer processes
lic
cannot occur but the compounds containing the phenyl groups are easily decomposed through the
reductive elimination path.
C
The mechanism of reductive elimination and factors favouring the process have been discussed in
detail in Sec. 10.7. The reverse reaction is called the oxidative addition (cf. Sec. 10.6).
D. Binuclear elimination: It may also decompose the compound.
2[Bu 3PCuBu J~2PBu3 + n-e 4 HIQ + I-butene + 2Cu
9.16.2 Conditions for Stabilising the Sigma-Bonded Organometallics

The above discussion indicates that there are many reaction pathways to destroy the M-C(lll)
a-bonds. However, the stability of the M-R bonds in general follows the sequence:
R: - C _ CH ) o-substituted aryl) aryl) alkyl.
Depending on the nature of the metal centre, the heavier congeners form the stabler M-C bonds (Lf
Table 9.16.1.1). It follows the sequence: Ti-C <Zr-C < Hf-C; Mn-C <Re-C, etc.
Prevention of the elimination process: It can be attained by blocking the coordination sites by the
strongly bonding ligands like CO, CsHs, PR 3, bpy, etc. Examples of the alkyl/aryl organometallics
containing such ligands have been already given.
Using the substitutionally inert metal centres: The metal centres like Co(III), Rh(III), Cr(III) are
ry
kinetically inert in the ligand substitution reactions. Consequently, such metal centres are kinetically
inert in reducing the coordination number through the ligand dissociation and in increasing the
ra
coordination number through the ligand addition. The elimination reaction mechanistically requires the
addition/dissociation of ligands. Thus, the kinetically inert centres can provide the stability.
ib
The examples are: [CrMe3(THF)3], [Rh(Et)(NH 3)s]2+, [Pt(C 2Hs)CI(PEt3)2], etc.
yl
Maintaining the 18e rule: [MMe2] (M = Zn, Cd) attains the 14e configuration but in presence of a
suitable chelating ligand (specially with the 1t-acidic property), it can form the stable compound like
m
[M(bpy)Me2] having the 18e configuration.
Using the more electronegative alkyl or aryl group: Stability of the M-C bonds increases with
he
the increase of electronegativity of the alkyl or aryl group. In fact, the metal-aryl bond is stahler than
the metal-alkyl bond. The fluorinated alkyl or aryl groups are the better candidates to stabilise the
M-C bond. The representative examples are: lc
ea
th
e/
t.m
Using the heavier congeners: The M-C bond strength is stronger for the heavier congeners of the
transition metals (cf Table 9.16.1.1). This is why, the heavier congeners are the better choices to
stabilise the M-C bonds.
e
9.16.3 Synthesis of the Sigma-Bonded Organometallics

er
(i) Alkylation or arylation by the Grignard reagents

TiCl 4 + 4MeLi ~ TiMe4 + 4LiCI
H
CuX + RMgX ~ CuR + MgX 2

AuBr3 + 2RMgX ~ AuR 2Br + 2MgBrX
k
[CrCI 3(thf)3] + 3MeMgBr ~ [CrMe3(thf)3] + 3MgBrCI

lic
(ii) Alkylation or arylation by other metal alkyls/aryls

2WCl 6 + HgMe2 ~ 2MeWCI s + HgCl 2
C
2WCl6 + 3Al2Me6 ~ 2WMe6 + 6AI(Me)CI 2

it may be noted that aluminum alkyls generally do not transfer all the alkyl groups.
CuX + LiR ~ CuR + LiX
LnCl 3 + 3LiR ~ LnR 3 + 3LiCI
LnR 3 + LiR ~ Li[LnR4]
LnR 3 + 3LiR ~ Li 3 [LnR6]
(iii) Nucleophilic attack by a carbonylate anion on alkyl halide:
Na+[Mn(CO)s]- + CH 3I ~ [H 3C-Mn(CO)s] + Na+I-
[Re(CO)s]- + CH 3I ~ [H 3C-Re(CO)s] + 1-
~ ~
ry
R-C-X+[Fe(CO)2(r(.~p)J ~ R-C-Fe(CO)2(11 5-CP) + X-
- [ ]
ra
(iv) Oxidative addition:
ib
[lr(CO)CI(PPh 3)2] + Mel ~ [lr(CO)(CI)(I)(Me)(PPh 3)2]
yl
(16e) (18e)
m
F2
C--CF
he
[Fe(CO)sl + 2F2C = CF2 - - (OC)4Fel( I2 + CO
C--CF
F
2
2 lc
ea
It is believed that intermediate olefinic complex undergoes the oxidative couping.
/CF 2- C F 2
I
th
o +co Iy-
[(OC)3Fe (llLC 2F4) ] 2 - - (OC)4 Fe " "
e/
CF 2- C F 2
(v) Insertion reaction:

t.m
[Rh(-H)(NH 3)s]2+ + C 2H4 ~ [Rh(C 2Hs)(NH 3)s]2+

[PtCI(-H)(PR 3)2] + C 2H4 ~ [Pt(C 2Hs)CI(PR 3)2], R = Et
e
+co
LnM-R ----;.~ L M-C-R
er
n II
o
H
\ /
k
/c~c\ '" /
lic
LnM-R --.~ LnM- C", /

C
f'"
R
Note: Mechanistic aspects of the Oxidative Addition and Insertion Reactions have been discussed
in Chapter 10.
(vi) Elimination reaction:
+ CO
ry
[Ni(bpy)(02CPh)2] ~ [Ni(bpy)(Ph)2] + 2C02
ra
(vi) Using ylids:
[Ph 3PCr(CO)5] + CH 2=PPh 3 ~ [(OC)5Cr-CH2PPh3] + PPh 3
ib
(vii) 7t-a Transition:
yl
m
he
Nucleophilic attack by py
or H- on the coordinated
lc olefins; see Sec. 10.12.81
for details.
ea
/Me
(ll s -C H HOC) F e - C - H
5 5 2 ~
th
Me
e/
9.16.4 Metal Carbene (i.e. Alkylidene) and Carbyne (i.e. Alkylidyne) Complexes
t.m
CH b CHR, CR2 are the examples of alkylidene ligands and acting as the monohapto, 2e donor ligands,
they can form the M=C bonds giving rise to the carbene or alkylidene complexes. CH or CR
represents the alkylidyne ligands and acting as the monohapto 3e donor ligands, they can form the
e
M - C bonds (1 cr bond + 2 d-p n-bond) in the carbyne or alkylidyne complexes. These aspects have
er
been discussed in Sec. 10.3.

H
k
lic
C
Alkyl, Alkylidene and Alkylidyne ligands

in a single complex
9.17 ALKENE COMPLEXES

9.17.1 Introduction
Zeise's discovery: Pt(II)-ethylene complexes [PtCI 2· C 2H 4]2 i.e. [(1l2-C2H4)CIPt(J.!2-CI)2Pt(1l2-C2H4)CI],
i.e. [{ Pt(1l2-C 2H 4)CI(J.!-CI) }2] and K[PtCI 3· C 2H 4] . H 20, i.e. K+[Pt(1l2-C 2H 4)CI 3]- (Known as Zeise's
salt) are the earliest examples of organometallics. These were accidentally prepared (a case of Scien-
tific Serendipity) by Zeise, a Danish pharmacist.
Zeise obtained the cream yellow salt, K[PtCI 3 • C 2H 4] i.e. K+ [Pt(1l2-C 2H 4)CI 3]- by refluxing PtCl 2
and PtCl 4 in ethanol followed by the addition of an aqueous solution of KCI and HCl. Ethylene was
produced probably in the following reaction.
PtCl 4 + 2C 2H sOH ~ PtCI 2· C 2H4 + CH 3CHO + H 20 + 2HCl.
ry
(redox reaction)
ra
PtCI 2 · C 2H 4 + KCI----7 K[PtCI 3 • C 2H 4] i.e. K+ [Pt(1l2-C 2H4)CI 3 ]-
ib
Zeise's salt may be prepared by passing ethylene through an aqueous solution of K 2[PtCI 4] and HCl.
K 2[PtCI 4] + C 2H 4 ~ K[Pt(C 2H 4)CI 3 ] + KCl.
yl
When an ethanolic solution of K[PtCI 3 · C 2H 4] is treated with conc. HCI, the orange dimer
m
[PtCI 2(C 2H 4)]2 i.e. [{Pt(1l2-C 2H 4)CI(Jl-CI) }2] is obtained. The dimer dissolved in acetone gives
trans-[Pt(1l2-C2H4)2CI2] when treated with excess C 2H 4.
he
-
/I CI
lc CI
"'-p/
ea
+ cone. Hel 7' '" /
. . .~ Pt t
(in acetate
solution)
CI CI
th
e/
H, /H)
(>=<
t.m
- stands for C=C

H/ 'H
e
Olefinic complexes of Cu(I), Ag(I), Hg(ll) and Pd(II): These are the typically soft metal centres
and olefins with their n-systems are also soft. This gives the favourable condition of the soft-soft
er
interaction.
H
It is well known that CuCI can absorb ethylene and it is due to the complexation of ethylene with
Cu(I).
Cu(l) + C 2H 4 ~ [Cu(1l2-C 2H 4)]+
k
lic
Similarly, Ag(l) can absorb olefins and this method can b~ used for the separation and purification
of olefins. When olefins (generally contaminated by other hydrocarbons) are passed through an aqueous
C
solution of silver nitrate or perchlorate, crystals of AgX -(olefin)x (x = 1, 2) are obtained.
Aqueous solution of AgX olefin) AgX· (olefin)x

In the same way, AgCI0 4 - C 6H 6 can be prepared.
In fact, AgCI0 4 easily dissolves in benzene due to the complexation of Ag+ with C 6H 6 - AgCI0 4 -C 6H6
in a polymeric state crystallises and C 6 H 6 moiety acts as a bridging ligand.
- Ag+- C 6 H 6 - Ag+- C 6 H 6- (angular structure).
In the angular structure, C 6H 6 stands in such a way that one C = C bond interacts with one Ag+
centre while another C = C bond interacts with another Ag+ centre.
"':g~
~/
Ag+
ry
(X-; CIO~)
ra
In the bridging function of C6 H6, the hexagonal symmetry of C6 H6 is changed in such a way
that the x-electron density in the interaction region may be increased.
ib
CuAICl 4 interacts with C 6H 6 to produce CuAlCI4 • C6H 6 in which one C = C bond of C 6H 6 interacts
with Cu(I).
yl
m
he
lc
(CsH s moiety interacts with only one metal centre)
ea
9.17.2 Structure and Bonding in Zeise's Salt and Stability of Complexes formed by
th
R2C= CR 2 (cf. Sec. 14.7.5 and Figs. 14.7.5.5-7, Vol. 3; for details)
e/
These aspects have been discussed in detail in Chapter 14 (Vol. 3). The important features of the
bonding mechanism (Dewar-Chatt-Duncanson, i.e. DCD model) are:
t.m
(i) electron pair in the n-BMO of ethylene is donated to the vacant dSp2 hybrid orbital of Pt(II) to
form a Jl-bond (a special type of a-bond); (ii) the vacant n*-MO of ethylene receives back electron
from the suitable d or dp hybrid orbital of Pt(II); (iii) these two bonding interactions are interdepend-
ent (i.e. synergistic action), (iv) C 2H 4 molecule remains perpendicular to the PtCl3 plane, but this
e
perpendicular orientation is not the essential condition for the DCD type bonding interaction; in fact,
er
the fluxional behaviour (in terms of PMR signal) of the C 2H 4 moieties in [(1l5-Cp)Rh(C 2H 4 )2] suggests
the rotation of the alkene about the metal-alkene complex; (v) the DCD model explains the elonga-
H
tion of the C-C bond in the coordinated C 2H4 due to the loss of n-bonding electron and gain of
electron in the n*-MO (cf. 137 pm vs. 133.5 pm).
k
lic
H
C
vc=c = 1623 em -1 in free C2 H4

vc=c = 1526 em -1 in Zeise's salt anion
H C 215pm
H
Fig. 9.17.2.1 Structural parameters of the anion of Zeise's salt K[Pt(C 2H4 )CI:d. C-C segment perpendicular to the
PtCI3 plane. Note: In the different alkene complexes, vc=c may be lowered upto 1410 em-I.
lXZ HfH
,~\Q
ry
ra
ib
H H
r
Fig. 9.17.2.2 Bonding in [Pt(C 2H4 )CI 3 (Dewar-Chatt-Duncanson, i.e. DCD model). Jl(i.e. 0) bond: n b (C 2H4) ~ dSp2
yl
(Pt) and 1t-bond: dxz or dp hybrid(Pt) ~ n*(C 2H 4 ). PtCI3 moiety in yz-plane; C-C segment (along the x-axis) perpen-
m
dicular to the PtClrplane (see Sec. 14.7.5, Vol. 3).
he
Pt-..I.r--+--I
lc
ea
-~~~---+---Z
th
y y x
dyz ---+ IT·
e/
(a) (b) (c)

t.m
Fig. 9.17.2.3 Rotation of the ethylene molecule around the Pt-C 2H4 a-bond axis. (a) C-C bond (along the x-axis) of
C 2H4 is perpendicular to the yz-plane containing PtCI 3 ; (b) C-C bond of C 2H4 in the plane of the PtCl 3 portion; (c) Static
structure of [(n5-Cp)Rh(C2H4hJ showing two types of protons-inner and outer denoted by i and 0 superscripts
respectively (see Sec. 14.7.5, Vol. 3).
e
er
x X
"c! NC CN
(Oxidative addition
H
M+-II Ph P"
3
,/
<;1
of olefin)
(OS = n) /C" Pt-II Ph 3 P C(CN)2
X X Ph p/
k
3 /C, 'Pt/I
Ph 3 P/ 'C(CN)2
lic
NC CN
(a) (b)
(Olefinic complex) (Metallacyclopropane (a) (Not acceptable) (b) (Acceptable)
C
complex)
Fig. 9.17.2.4 Equilibrium between the olefinic complex (a) and metallacyclopropane complex (b). Note: For the
strong 1t-acceptor olefins like C 2(CN)4, the C-C n-bond in the complex is almost completely destroyed favouring the
metallacyclopropane complex. This aspect has been discussed in detail in Sec. 14.7.5. Vol. 3.
Ligating behaviour of C 2H 4 vs. C 2F 4, C 2 (CN)4: Compared to C2H4 , the other two olefins are the
weaker a-donors but the better n-acceptors. Sometimes, the strong n-acceptance may lead to the
metallacyclopropane complex rather than the olefinic complex (cf Fig. 9.17.2.4). Experimental evidences
support the fact that the 1t-acceptor ability is more important than the a-donor ability to determine
the overall strength of the metal-alkene bond. These aspects have been discussed in Sec. 14.7.5, Vol. 3.
Ph P CO .", R
CR 2K 3~-L ~7""'" R
[lr(CO)CI(PPh 3)2l + II ~ ~ ./ Itr ,.--:;:ry/
CR ,.".,." C~ R
(Vaska's complex) 2 Ph3~ CI \
R
ry
ra
ib
Veo (cm- 1) : increasing trend) (2057 cm- 1 for the C 2 (CN)4 adduct)
yl
Fig. 9.17.2.5 Relative ligating power of the different olefins having the different 1t-acceptor abilities.
m
The vco values of the Vaska's complex and its adducts of O 2, C 2F4and C 2(CN)4 are: 1967 cm- 1, 2052
cm- 1 and 2057 cm- 1 respectively. The higher vco values in the adducts indicate the more positive
he
charge on the Ir-centre and it disfavours the Ir~CO (i. e. d ~ 1t *) 1t-back bonding.
lc
9.17.3 Complexes with Polyolefins-Both Conjugated and Isolated Double Bonds:
Complexes with the Chelating Dienes
ea
The representative examples of chelating polyolefins are:
o
th
e/
o i.e.
t.m
i.e. H2 C = CH - CH = CH 2
(Butadiene) (Cyclopentadiene) cis, cis-cycloocta-1-5-diene
(1, 5-cod or cod)
e
o
er
H
i.e.,
k
lic
1, 3, 5, 7-cyclooctatetraene
Norbornediene
(1, 3, 5, 7-cot or cot)
C
(nbd)
Examples of complexes with the chelating dienes are given in Fig. 9.17.3.1.
MO(CO)4
[MO(CO)4(nbd)]
MO(CO)4
[MO(CO)4(cod)]
ry
ra
ib
yl
m
MO(CO)2
he
lc
ea
-4CO
th
[Rh(CO)2C1]2 + CaH 12 (cod) ..

e/
CI
/""
t.m
Rh Rh
""/ CI
e
Fig. 9.17.3.1 Some representative complexes with chelating dienes or di-olefins.

er
It is evident that the diolefins (i.e. dienes) can act as the chelating ligands and consequently they
H
can form more stable complexes than the mono-olefins. In fact, only few complexes with the mono-
olefins are known while a large number of complexes with the diolefins are well known. Diolefins act
as the 4e-donor ligands. Here it may be mentioned that sometimes, the polyolefins may act also as the
k
2e-donor ligands (i.e. behaving like monoolefins). In fact, cot, can function as a 6e donor ligand to a
lic
metal centre, i.e. three olefinic bonds participate. It can act also as a 4e donor to one or two different
metal centres. These aspects will be discussed later.
C
Bonding by the isolated olefinic bonds: Isolated double bonds coordinate with the metal centre just
like the monoolefins as in Zeise's salt anion.
Bonding by the conjugated dienes: In this regard, butadiene as 114-C4H 6 is the classic example in
the complex [Fe(CO)3(1l4-C 4H 6 )].
[Fe(CO):;] (18e) + C 4H 6 ~ [Fe(CO)1(1l4-C 4H 6 )] (18e) + 2CO
In [Fe(CO)5]' two CO groups are replaced by C'4H 6 and the 18e configuration is ¢aintained. Thus,
C4H 6 acts as a 4e donor ligand.
MO picture and coordinating beha"iour of butadiene: Before discussing the coordinating behav-
iour of 114-C4H6 , we are to consider the structural features and MOs of the free butadiene.
145 pm
H 2C=CH--CH=CH 2 H 2C=CH 2
136pm 136 pm 134pm
In free butadiene, the terminal C-C bond length is slightly longer than the isolated double bond and
the central C-C bond is significantly shorter than the isolated C-C single bond.
Free butadiene can have two geometrical isomers, i. e. s-cis- and s-trans. Here, s denotes the geometric
ry
isomerism with respect to the central single C-C bond. The tran-form is more stable than the cis-
ra
form by about 12 kJ mol-I (cf Sec. 12.5.5; Fig. 12.5.5.5). Between the s-trans and s-cis-forms, the
s-cis- form is more suitable for acting as the 4e-donor 114-C4H6 ligand. The s-cis- form may have the
ib
canonical forms as shown in Fig. 9.17.3.2. In the same way, the's-trans form may also have the different
canonical forms.
yl
~i.e.,
m
,,
,,
,r----
n '\
he
J
,,
'\
~- F\ +
~+ F\ - i.e., /,'
~\\
(s-trans form)
lc (s-cis form)
ea
(a) Different forms of butadiene
th
H H
e/
t.m
~sp3-C
(II) (III)
(n+2)+
e
(Mas M )
er
(b) Possible ways of binding of s-cis-butadiene (c) Possible way of binding of

s-trans-butadiene.
H
Fig. 9.17.3.2 (a) Different forms of butadiene. (b) and (c) Different ways of binding of butadiene in metal complexes.
Note:. In I, the terminal C-C bonds are expected to be smaller than the central C-C bond while
k
in II, the central C-C bond is expected to be shorter than the terminal C-C bonds. It
lic
happens so (i.e. II) in [(CP)2Zr(1l4-2, 3-Me2C4H4)].

• I is the most common mode of coordination by butadiene.
C
• In II, it may be assumed that the charge separated canonical forms of s-cis-C 4 H 6 are coordi-
nating. Here the terminal C-atoms form the classical M-C a-bonds while the double bond
between the central C-atom coordinates just like the ethylenic double bond.
In most of the cases, butadiene as s-cis-C 4 H 6 coordinates in the fashion I shown in Fig. 9.17.3.2. By
using the four p-orbitals (one in each C-atom), we can construct 41t-MOs for cis-butadiene and 4
electrons are placed in the lowest two 1t-MOs (\Ill and \112) i.e. 1t 12 1t2 1t3o 1t40. The \Ill and \112 MOs can
act as the donor orbitals and \113 and \114 can act as the acceptor orbitals. However, in terms of energy,
'112 (i.e. HOMO) is the most" suitable one to act as the donor orbital and similarly, '113 (i.e. LUMO)
is the most suitable one to act as the acceptor orbital.
'112 (i.e. HOMO): bonding interaction in the terminal C-C bonds; antibonding interaction in the
central C-C bond.
'113 (i.e. LUMO): bonding interaction in the central C-C bond; antibonding interaction in the
terminal C-C bonds.
ry
ra
ib
yl
m
he
lc
ea
th
e/
t.m
e
er
H
1t t i.e. 'V t: 2pZ<C t ) + 2pz(C 2 ) + 2piC 3) + 2pz(C 4 )

k
1t2 Le. 'V2: 2pz<C t ) + 2pz(C 2) - 2piC 3) - 2pz(C 4) (Assuming the xy-plane
lic
1t3 i.e. 'V3: 2piC t ) - 2pi C 2) - 2piC 3) + 2pi C4) as the molecular plane)
i.e. 'V4: 2piC t ) 2pZ<C 2) + 2piC 3) - 2pz\C 4)
C
1t4 -
Fig. 9.17.3.3 1t-Molecular orbitals in cis-butadiene (see Vol. 1 for details of the MOs of butadiene).
Now let us consider the effect of electron donation from 'V2 and electron acceptance in 'V3.
'112(C 4H 6 ) ~ d(M): removal of the bonding electron from the terminal C-C bonds will elongate the
terminal C-C bonds; removal of the antibonding electron from the central C-C will shorten the
central C-C bond.
d(M) ~ '113(C 4H 6 ): increase in the bonding electron density for the central C-C bond will shorten
the central C-C bond; increase in the antibonding electron density for the terminal C-C bonds will
elongate the terminal C-C bonds.
It may be mentioned that 'V 1(C 4H6) ~ M will equally affect all the C-C bond because 'V 1 is bonding
in nature for all the C-C bonds. In fact, 'V 1 ~ M will lead to removal of bonding electron and it will
elongate all the C-C bonds equally. However, this donation is less important than the
'112(HOMO) --+ M donation because 'Ill is of much lower energy.
By considering the effects of'V2(HOMO) --+ d(M) and d(M) ~ 'V3(LUMO), we can conclude that
in the coordinated C4H 6, the terminal C-C bonds will be elongated and the central C-C bond will be
ry
slightly shortened. This prediction is qualitatively supported in the experimental findings. How-
ever, it may be noted that the central C-C bond length does not practically change. But in the other
ra
conjugated diene complexes (e.g. 4e donor methlcyclopentadiene), the predicted slight shortening of
the central C-C bond is experimentally supported.
ib
145pm
145pmffi145
yl
145pm pm C10
136pmn ~
m
1210pm
vr- co
he
Fe(COb
co
lc
All Fe-C (butadiene) bonds are equal (- 210 pm)
ea
[Note: To explain the no change in the central C-C bond length after metal coordination, some authors
have suggested that probably the structures I and II of Fig. 9.17.3.2 contribute equally. However, the
13C-NMR does not support the structure II where the terminal C-atoms are in sp3-state].
th
Here it may be noted that C4H6 can act also as a 2e donor, i.e. only one C=C bond participates in
e/
the bonding interaction just like the ethylene. One such such example is: [Fe(CO)4(C 4H6 )], i.e.
[Fe(CO)4(1l2-C 4H6)].
t.m
When the s~trans-C4H6 (cf. Fig. 9.17.3.2) acts as a 4e donor ligand, then it acts as a dihapto
(1l2) ligand through the two end-carbon atoms. In such cases, the double bonds act as the isolated
double bonds and each double bond separately coordinates (i.e. 112, 112-C4H6). One such example is
[(lls-Cp)2Zr(1l4-1, 4-Ph2C~H4)]. Such 114-butadiene (i.e. 112, 112-C4H6 ) ligand may be easily converted
e
into 112-butadiene to produce the coordinatively unsaturated compounds which are highly reactive.
er
9.17.4 Common Routes of Synthesis of Olefinic Complexes

H
(i) Direct interaction between the olefin and metal halide or metal carbonyl:
Y- + C H l2 (cod)
k
K2[PtC1 4] + C 2H4 ~ K[Pt(C 2H4)C1 3] + KCI; [PtC1 4 g -2Cl- )[PtCI 2 (cod)]

lic
C
.../
[Fe(CO)s] + C4H6 -2eo ) [(1l4-C 4H 6)Fe(COh], i.e. [Fe(COM1l 4-C4H 6)]; (>t CO
e-
co
co
ry
ra
o
ib
(llCC 4 Hs ) II ( -C H )
n4
yl
-4CO )
""" /C"" /" 4 S
m
/C~/C~
OC C CO
he
II
o
[PdCI 2(PhCN)]2 +nbd(C 7 H s ) -2PhCN )[PdCI 2(nbd)]
lc
ea
Other examples are shown in Fig. 9.17.3.1.
(ii) Reductive addition: The commonly used reducing agents are Li, hydrazine, NaBH4, AIBuj, etc.
th
[(115-Cp)2ZrCI2] + 2Li + C4H6~ [(115-Cp)2Zr(114-C4H6)] + 2LiCl.

e/
[ (Ph 3 P )2PtC12 J +C
2
H
(N 2 H 4 +EtOH)
4
) [(Ph 3 P) Pt (C 2H 4
2
)J + 2CI-
t.m
[ Ni (acac)2 ] +C g H 12 (cod)
(AIBu;) ) [Ni(cod)2]
Sometimes, ethylene can itself act as the reducing agent. One such example is illustrated bellow.
e
er
H
+acacH
-------3~~ [Rh(acac)(C 2H4 )2l
-Hel
k
(16e)
lic
~COd)Rh <::>
C
• Rh(COd)]
Na+Cp-
-------3~.
[
Rh(Cp)(C 2 H4 )2
] l (16e)
(18e)
Here in presence of the ligands like acac, Cp, etc. the chloride bridges are ruptured.
(iii) Condensation of metal vapours in presence of alkenes:
+CgHI2 (cod) [ ( ) ]
Fe ( vapour ) -----~) Fe cod 2
(condensation)
9.17.5 Reactivity of the Coordinated Alkenes (cf. Sec. 10.12.81)

The presence of loosely bound 1t-electrons in the free alkenes repells the approach of the nucleophiles
but favours the approach of the electrophiles. In fact, the free alkenes can easily experience the
electrophilic attack. But in the coordinated alkenes, this 1t-electron cloud is used in making the
a-donation to the metal. Thus, the electron density in the coordinated alkene is significantly
reduced to favour the approach of a nucleophile. In fact, the nucleophiles like -OH, H20, -OMe,
ry
MeCOi, CI-, etc. can attack on the coordinated olefin.
ra
[P t (C 2 H 4 ) CI 3 ]- + H 2 0 standi~g ) H CCHO + Pt(O) + 2H+ + 3CI-
(or,heatmg) 3
ib
Zeise's salt anion, [Pt(C 2H4 )CI 3]- on standing in water slowly gives CH 3CHO and Pt-metal. It is due
to the nucleophilic attack by H 20 on the coordinated ethylene. The corresponding Pd-complex
yl
is more reactive and this is the basis of conversion of C 2H4 into CH 3CHO in Wacker Process (see
m
Chapter 10).
he
Silene Complexes
It has been already discussed that the silenes, R 2Si=SiR2 are stable for the bulky R-substituents.
lc
R 2Si=SiR2 is a better a-donor ligand because the HOMO (a 1t-BMO) is of higher energy (compared
to that of an alkene) and also a better 1t-acceptor because the LUMO (a 1t*-MO) is of lower energy
ea
(compared to that of an alkene) (cf. Fig. 14.7.5.8, Vol. 3). Thus, silene is expected to act as a better
1t-acid ligand to form the complexes. One example is:
th
R" /R P\ /Ph
e/
p
SI{__
I pt/ )
(R=Pr
i
)
t.m
SI P
· "
R/ \R pi "Ph
e
In this process, the crucial step is the nucleophilic attack on the coordinated ethylene with Pd(II) to
give the a-bonded compound, Pd II -CH 2CH 20H which then participates in the subsequent reactions
er
(see Chapter 10 for details).

H
H H
_C_2_H4~. .. _~
-
Pd '_I _O_H_~.... Pd"-CH2CH20H ~ - - _

k
H H
lic
9.17.6 Fullerenes as Ligands and Fullerene Complexes (cf. Sec. 10.11.5, Vol. 2)
C
C 60 , C 70 fullerenes may be considered as the electron deficient alkenes or arenes and generally they
form the complexes as the dihapto-ligands, i.e., 112-fullerene. In this dihapto mode of coordination to
the transition metal centre, the C=C bond at the fusion of two six membered rings participate. In such
complexes of 112-fullerene, the coordinating C-atoms are slightly pulled away from the fullerene sur-
face. Electron acceptance in the 1t*-MO elongates the C-C distance as usual. Such complexes bearing
the 112-fullerene are commonly synthesised through the displacement of other ligands. It is illustrated
in the following reaction.
[(11 2 --e 2 H 4 )Pt(PPh 3 )zJ + C 60 ~C2H4 + [(11 2 --e 60 )Pt(PPh 3 )zJ
ry
ra
Fig. 9.17.6.1 Structure of [(1l2-C 60 )Pt(PPh 3)2].
Sometimes, fullerenes can directly bind to the vacant coordination sites.
ib
CI
yl
r;: c" I/PPha
~ol
m
/Ir"
C I PPh 3
he
CO
Other examples of complexes containing the 112-fullerenes are:
lc
[(11 2 -e 6o )Fe(CO)4 J, [(11 2 -e 60 )Mo(11 5 -e 5H5 )zJ, etc.
ea
The C 60 and C 70 fullerenes can also bind as 112,1l2-fullerene and 112,1l2,1l2-fullerene in some com-
plexes. In [Ru3(CO)9(J.l3-112,1l2,1l2-C6o)], the C-C bonds bridging the Ru-centres are slightly shorter
th
than the other C-C bonds present in the six-membered rings. This observation can be better explained
by considering the 112,1l2,1l2,-C6o mode of coordination rather than the 116-C 6o mode of coordination.
e/
However, there are also examples where C 60 fullerene coordinates as 116_C 60 or lls-C 6o .
t.m
By using the substituted fullerenes like C6oMeS, C7oMe3, etc. a metal ion may be sandwiched between
a lls-CsHs ring and a lls-fullerene. One such example is: [(lls-CsHs)Fe(lls-C7oMe3)]. The methyl groups
bonded to the C-atoms of the five membered ring which binds to iron, probably stabilise such complexes
by their electron pushing effect.
e
[(Et3P)2Pt]6C60 is a spectacular complex where six (Et3P)2Pt units are octahedrally attached to the C 60
er
fullerene surface.
H
Me
~Me
\ l~SJMe
k
o/~~01 Me
lic
~Me
C
Me
Fig. 9.17.6.2 [(C 60)(OS04)( 4-t-butylpyramidine)].

Other types of fullerene complexes: Adduct formation to oxygens of OS04 e.g.
[C6o(Os04)(4-t-butylpyridine)2; endohedral complexes, e.g. La3+ @ C 603- i.e., La @ C 60 or simply
LaC 60 , La @ C 70 , U @ C 60 , etc. where the metal ion is completely encapsulated within the fullerene
sphere; intercalation compounds, e.g. MC 60 , M 3C 60 , M 4C 60 , etc. where the alkali metal ions (M+)
occupy the octahedral/tetrahedral sites of the close packing structure of C 60 . These are discussed in
Sec. 10.11.5 (Vol. 2).
9.18 ALKYNE COMPLEXES

9.18.1 Coordinating Behaviour of Alkynes
Alkyne (RC==CR) possesses C-C one a-bond, and C-C two n-bonds. These two n-bonds are
mutually in perpendicular directions. In terms of MO, the n-MOs may be described as follows (by
taking x-axis as the C---C a-bond axis).
ry
2py + 2py ~ n y (BMO) and n; (ABMO)
ra
2pz + 2pz ~ nz (BMO) and n; (ABMO).
The 4 n-electrons are placed as:
ib
yl
m
Alkynes (RC == CR) can bind as the n-acid ligands just like the alkenes (R2C = CR2). RC CR ==
he
can use the filled n-BMOs (i.e. HOMOs) for a-donation and n*-ABMOs (i.e. LUMOs) for
metal ~ ligand n-acceptance in different possible ways. These are discussed bellow.
lc
(a) As a 2e-donor ligand like an alkene: In this mode, one pair of n-MOs (i.e. ny and n; or nz and n;,
ea
taking x-axis as the C-C axis) is involved in the metal-alkyne interaction. In this mode, other pair of
n-MOs remain unperturbed. Thus, the alkyne acts just like the alkene, i.e. the filled n-BMO is used for
a-donation to the metal centre and the corresponding vacant n* is utilised in metal ~ alkyne back
th
bonding. It can be represented as follows:

e/
_1 R
t.m
R
I
7
C cr-bon C;! 135-150°
n
_III . . .E---~.,.
e
M + 4 : M (n+2)+ '---"""'125-130 pm
~
er
C -b C (Oxidative addition
on -'" product)
H
1 (J
R R
k
(I) Alkyne Complex (II) Metallacyclopropene

lic
An alkyne is more electronegative than an alkene (cf. sp-C is more electronegative than sp3_C). This
C
is why, an alkyne is a better 7t-acceptor than an alkene. Thus, the coordination of RC == CR (as a
2e donor ligand) very often leads to the metallacyclopropene complex. Here it may be mentioned that
for the alkene complexes, the possibility of the formation of metallacyclopropane complex
arises for the alkene which acts as a very good n-acceptor ligand. It happens so for the ligands like
(CN)2C = C(CN)2o This aspect has been already discussed (Sec. 9.17.2 and Ch. 14, Vol. 3). In fact,
when metal ~ alkene/alkyne 1fi-back bonding is very much efficient, the C-C 1fi-bonding is almost
completely lost.
In fact, the complex, [Pto(PPh 3)2(PhC==CPh)] is an example of metallacyclopropene complex
where the Ph-groups are bent back by about 40°.
ry
vc-c = 1750 cm- 1 (in the complex)
== CPh)
ra
1
V c _c = 2200 cm- (in free PhC
ib
PhC == CPh has been found to act as a 2e-donor ligand in [(Ph3P)2Pto(PhC==CPh)].
yl
However, when the metal ~ alkyne back bonding is not so efficient then the alkyne complex (rather
than the metallacycloproprene complex) is reasonable to be argued (ef Sec. 9.17.2 and Ch. 14, Vol. 3).
m
It happens so for [Pt IICI 2(P-toludine)(Bu t-C==C-Bu t)].
he
lc
ea
NH 2
I
th
(cf.- C - C - bond length

CI-Pt-CI ::::: 120 pm in the free alkyne)
~
0
20
e/
-(-yc C\------
t.m
0
Bu' \.160 Bu'
-124 pm
In the above complex, the But-groups are bent back by only 20° and C-C bond is not significantly
e
elongated. All these data indicate that in the present complex, the metal ~ alkyne back bonding is not
er
efficient. It is also reasonable because Pt(II) is more reluctant to act as a n-donor centre (compared
to Pto).
H
(b) As a 4e-donor ligand to one metal centre: In this mode of coordination, all the 4n-MOs
participate. Two orthogonaln-BMOs (i.e. HOMOs) participate in a-donation to the metal centre, and
k
two n*-ABMOs (i.e. LUMOs) participate in metal ~ alkyne' n-back bonding. One pair of the n-MOs
lic
CR
can interact just like an alkene to produce the three membered ring M(II .
The other n-bonding
C
CR C
electron pair may be donated to a dn-orbital that should be aligned perpendicular to the M( I plane.
C
The corresponding vacant n*-MO of the alkyne can participate in back bonding through the 8-type
C
bonding. If the pair of n-MOs to constitute the M( I ring is labeled as n(II) and n*(II) then the other
C
pair of n-MOs may be labeled as nCl) and n*(l..). The bonding interactions are:
Path!: 1t(II)~M, M~1t* (II)} if. F' 9 18 1 1

8 * c. 19. . . .
Path2: 1t(1)~M, M~1t (1)
It has been proved that the metal-alkyne interaction through the Path 2 is less efficient than that
C
I ring.
ry
occurring in the Path 1 leading to the M/
"C
ra
H
ib
8i0
yl
m
1t u(2pz)
he
d Z 2(M) _ 0 _ 1tu(2pz)(C 2 H2 )
dyz(M) ~ 7t u (2py)(C 2 H2 )
i.e·,1tIl~M(d)
i.e.,1t.l ~M(d)
(a-type interaction)
(a) x
lc (1t-type interaction)
~z
(b)
ea
I_ denotes C-atoml
th
y
e/
QP0 10
t.m
ciBOI<8
e
( H ;
d xz 1t; (2pz)
er
dxz(M) ~ 1t;(2pz)(C 2 H2 ) dxy(M) -4 7t; (2py)(C 2 H2 )

(1t-type interaction)
H
(8-type interaction)
M~1t~
M -41t1
(c) (d)
k
Fig. 9.18.1.1 Different possible pathways for alkyne 1t-HMOs to metal electron donation and metal to alkyne n-ABMOs
lic
electron pushing.
The 1t(II)~M and 1t(..lJ~M donations explain the 4e-donor property of an alkyne. It is
C
represented as:
Obviously when an alkyne (RC~CR) acts as a 4e donor ligand, the C-C bond length should be
more elongated and the R-grounds should be more bent back compared to the case where the alkyne
acts as a 2e-donor ligand.
~ R a
C>/R
1 1
iY
C C- - - - - - - _.
M(IIJ"'x M~IIJ"'y C-e bond length: y> x;a > P
ry
C C-----
~R ~R
ra
1a
1
(2e donor RC== CR) (4e donor RC_ CR)
ib
Alkynes may coordinate as a 4e donor ligand to the metal centres having the fewer d-electrons. Such
centres are: MOll and W II of if-systems.
yl
Here it is worth mentioning that donation of the n-bonding pair (from the n(.l)-BMO) to the
m
dn-orbital is not so efficient compared to the a-donation from the n(II)-BMO. The acceptance in the
n*(.l) from the metal centre through 8-bonding is almost insignificant. Thus electron counting assuming
he
the 4e donor property of alkyne is called in question.
(c) Alkynes as the bridging ligands: Alkynes can act as the bridging ligands in different ways. For
lc
the bridging alkynes, both pairs of n-bonding electrons are very often involved to coordinate with two
metal centres. The common modes are shown in Fig. 9.18.1.2.
ea
Ph
-1 8 p m
R
r R 130-135 pm R /
""nIXI"
~C Ph--1\
th
4°:0c=:L C~ _40 ~CR

R (/ c
RC1\
0
e/
/ \ i.e.,
C _
t.m
M M M--M M--M Ni Ni
ll, Jl -mode ;
2 (a-complex) (115- /Cp ) " (115-Cp)
(2e-donor)
(1t-complex)
e
(a)
R
er
R / /R
"'pY;1
H
R"/p(/1
A
k
I' ,I
"" / "" "" / ""

oC-Co'--co-co ie oc-co--co-co
lic
/
oc coco co
. ., oc
/ coco co
C
(b) (11 2 , Jl2-mode (4e donor)

Fig. 9.18.1.2 Alkynes as the bridging ligand
Note: In the 11 2, J.!2-mode of alkyne as a 4e-donor ligand, the C-centres are almost in a tetrahedral
geometry.
9.18.2 Common Routes of Synthesis of the Alkyne Metal Complexes

Generally by direct addition of alkynes, their complexes are prepared.
[C0 2 (CO)s] + PhC==CPh~[ CO 2 (CO)6 (Ph 2 C 2 )J + 2CO; (Structure shown in Fig. 9.8.1.2.)
[Ir(CO)CI(PPh J )2] + RC=CR ---7 [ Ir(CO)CI (PPh J )/1'1 2-RC==CR) J; (oxidative addition)
[Pt(PPh J )2(olefin)] + PhC==CPh -olefin >[ Pt(PPh )/rI 2- PhC ==CPh)]
J
(PhC==CPh acts as a 2e donor ligand)
ry
[Mn(1l5-Cp)(COh]+RO=CR -~o >[ Mn(1l5-Cp)(CO)2(R 2C2)]
ra
Note: If in RC==CR, R is not a bulky group, the corresponding complexes are more stable. Sometimes,
ib
instead of the alkyne complex, polymerisation of alkynes may be noted.
yl
Ph Ph Ph
Ph
m
[Fe(CO)J + PhC-CPh ~ Fe(CO)3'O=C Fe(COb etc.
he
Ph
Ph Ph Ph
lc
ea
Me
Me Me
MeC==CMe
th
[Ph 3Cr(thf):J ~ ~1----CrPh3

-thf
Me Me
e/
Me
t.m
HC CH
== T tetramerisation
e
ofC 2 H2
·w
CH ----.~
4CH
'Y(I~Ni~ v~ • Cyclooctatetraene
er
H
HC CH
k
lic
Ni(CNI)2
C
9.18.3 Reactivity of the Coordinated Alkynes (cf. Sec. 10.12.8)

Like the coordinated alkenes, the coordinated alkynes are also sensitive towards the nucleophilic attack.
It is illustrated in the following reaction.
[ (ll5-Cp)Fe(CO){p(OPh hl] (1l5-Cp)Fe(COHP(OPh h}

..
+
-MeLi
I
+
I /Ph + Li+
MUCPh Me-c=c",
Me
9.19 ALLYL COMPLEXES

The allyl group C 3Hs (i.e. CH 2=CH-CH 2) can be viewed as the C3Hs- anion or C 3Hs radical, when
bound to the metal centre. As C 3Hs-, it may function as either 2e-donor or 4e-donor. Similarly, as a
C3H s radical, it can function either as 1e or 3e-donor.
Mn+-C 3H s (as C 3H s radical)
ry
M(n+I)+-C 3Hs (as C 3Hs- anion)
ra
H
ib
I
c
yl
/.,~
> H2C' I 'CH 2
m
..,I-c3Hs (1 e or 2e donor) M
he
(a-allyl)
l -.. . . _------------)
V
lc ..,3_ C H (3e or 4e donor)
3 s
(7t-allyl)
ea
9.19.1 Coordinating Behaviour of the Allyl Group

th
For the sake of simiplicity, here we shall consider the allyl group as C 3Hs- which will act as a 2e-donor
e/
ligand in the M(llI_C 3Hs) or M(a-C 3Hs) fashion or a. a 4e-donor ligand in the M(1l3-C 3Hs) or
M(1t-C3Hs) fashion.
t.m
In terms of VBT, the resonating structures of C 3Hs- group are:

e
er
H
Thus the 1t-electron cloud (i. e. 41t-electrons) is delocalised over all the three C-atoms.
k
lic
In terms of MOT, we can construct three 1t-MOs by using the three p7t-orbitals (each C-atom providing
one p7t-orbital) of the C-atoms. If the C-C and C-H a-bonds lie in the xy-plane then the pz-orbitals
C
are available to construct the three 1t-MOs (see Fig. 9.19.1.1).

The four pi-electrons are placed in the lowest two 1t-MOs, i.e. 'VI and 'V2. Thus 'V2 is the HOMO and
'113 is the LUMO. To act as a 4e donor ligand, both the filled 'V I and 'V2 MOs will participate in
donating the electrons to the metal centre. These are shown in Fig. 9.19.1.1. The electron donation and
n-acceptance are as follows:
~
~dxz x
)-.Z
ry
'V3
3
•
ra
ib
yl
m
'VI: 't'2p;:(C I ) + 'V2p;:(C 2) +
he
'V 2p;:(C 3)
lc 'V2: 't'2p;:(C I ) ± 'V2p;:(C 2) -
ea
'V 2p;: (C 3) == 'V 2p;: (C I ) - 'V 2p;: (C 3)
~d2' 'V3: 'V2p;:(C 1) - 'V2p;:(C 2)

th
+ 'V 2p;: (C 3 )
Suitable metal d-orbitals
pz-AOs which can effectively AO of C 2 does not participate in the
e/
'V1
IT-MOs overlap with the IT-MOs of construction of'V2- MO because the
of Allyl ligand the allyl ligand
t.m
vertical nodal plane passes through

the C 2-atom.
Fig. 9.19.1.1 n-MOs of the allyl ligand and suitable metal d-orbitals for interaction with the n-MOs of the allyl ligand.
e
The 1t-acceptance is not significant. When the 'V I and 'V2 MOs act as the donor orbitals, the
er
113-C 3Hs mode is attained and all the C-C bond lengths should be the same in the complex. This
H
prediction has been supported in most of the cases. However, in some rare cases, different C-C bond
lengths have been recorded, e.g. [(llS-Cp)Mo(NO)(C 3Hs)] shows the C-C bond lengths as 142 pm and
137 pm. It supports the following structure.
k
lic
C
(One Mo-C single a-bond, another bond developed by the coordination of the olefinic C=C bond
in the usual 112-fashion).
9.19.2 Possible Stereoisomerism in the Allyl Complexes

PMR spectra have suggested the cis- and trans-forms of diallylnickel, i.e. [Ni(1l3-C 3Hs)2].
(cis-isomer) (trans-isomer)
[Ni(1l3- C3Hs)2] in solution.
ry
Syn and anti-isomers for the substituted allyl complexes are also known. This is illustrated for
R-C 3H4 group (R = CH3, C2H s etc.).
ra
. ", R~"", M
(%
M
ib
.. .. \ ", \
\ \
\ \
yl
R
m
(Syn-isomer) (Anti-isomer)
The syn and anti forms for l-methylallyl complex, e.g. [Co(CO)3(113_CH3-C3H4)] have been noted.
he
9.19.3 Fluxional Behaviour in the Allyl Complexes
lc
In a trihapto-allyl complex, i.e. 113-C3HS' with respect to the position of the H-atom attached to central
C-atom, there are two types of terminal H-atoms called syn- and anti-H atoms.
ea
H H
I I
th
HSY":I~c/Hs
,,, I Hy(syn) C
""r~c/
H (syn)
e/
i.e. ' I ,
t.m
Ha M Ha (anti) H M H (anti)
The fluxional property arises from the rapid interconverting structures of the complex through the
11 3-11 1-11 3 path. This aspect has been discussed in detail in Sec. 10.11.
e
er
9.19.4 Some Representative Examples of the Allyl Complexes

The examples are [Zr(C 3Hs)4], [V(C 3Hs)3], [Mn(CO)(C 3Hs)], [CO(CO)3(C 3Hs)], [Ni(2-methylallyl)2],
H
[(11s-Cp)Mo(CO)2(C3Hs)], etc. The structural details of bis(113-2-methylallyl) nickel are given in

Fig. 9.19.4.1. It is a sandwich structured compound.
k
lic
C
(Ni is equidistant from three C-atoms)
Fig. 9.19.4.1 Structure of bis(n3-2-methyl-ally)nickel (trans-form); sandwich structured compound.

The structural features of the unsubstituted allyl complex, i.e. [Ni(1l3-C 3Hs)2] are given below.
Ni-C (terminal) == 203 pm, Ni-C (central) == 198 pm, C - C- C == 120.5°, C - C == 141.5 pm.
The terminal C-atoms are tilted towards the metal centre for making a better 1t-overlap. Here it is worth
mentioning the catalytic activity [Ni(1l3-C 3Hs)2] in cyclotrimerisation of butadiene.
ry
ra
ib
yl
C12H18
(cyclododeca-1, 5, 9-triene)
m
Here it may be mentioned that sometimes the 113-allyl moiety may be present in the rings. It is
illustrated below.
~\ he
lc
ea
OC-Fe Fe-CO
/ \CO
th
OC CO
e/
t.m
(The 7-membered ring of azulene is providing the 113-moiety while the 5-membered ring provides
the lls-moiety).
Here one double bond is involved in conjugation with the Cs-ring.
e
CsHs- (cyclopentadienyl anion) can act as 113-Cp- (i.e. 4e donor) similar to 113-C3Hs-. When Cp-
er
binds as 113-CP-, one double bond is kept free from coordination. The indenyl (Ind) ligand can easily
provide the 113-bonding function because the remaining double bond is involved in conjugation within
H
the phenyl ring.

k
@ Q 00
lic
M M M
C
3 3
5
(11 -CP) (11 -CP) (11 - lnd)
Se-donor 4e-donor 4e-donor
When the lls-Cp mode changes into the 113-Cp mode, the metal centre can accommodate a 2e-donor
ligand.
[(Tl 5 -Ind)2 V]e15e) +co) [( Tl 5 -Ind) (Tl 3-Ind) V (CO)2 ](17e)
In [(C 7H s)Co(CO)3], cycloheptatriene binds as a 113-functional moiety. Sometimes, the cyclo-

pentadienyl group may also behave in this way.
9.19.5 Common Routes of Allyl Complex Synthesis

(i) Using the allyl Grignard reagent: It is actually an example of metathesis reaction.
>
ry
ra
+ 2MgBrCI
2C 3 H sMgBr (Grignard reagent) + NiCl 2 ----:'(-~:-~:-~-:--)~ Ni
{~
ib
yl
m
(A sandwich type complex, [Ni(1l3-C 3H sh], (trans-form)
he
(ii) Nucleophilic attack of carbonylate on allyl halide:
lc
ea
-NaBr
)[(OC)s Mn(-CH 2 -CH=CH 2 )]
i.e., [(OC)s Mn (11 I_ C3Hs )]
th
-co1 Heating or hv
e/
[(OC)4 Mn(11 3 -C 3 Hs )]
t.m
-NaBr
)[(OC)4Co (-CH 2 -CH=CH 2 )]
e
l-co
er
hv
H
k
lic
-NaCl
>[ (11 s -Cp)MO(CO)3 ]
C
I
CH 2 -CH=CH 2
-CO 1 Heating or hv
[(11 S -Cp)MO(CO)2 (11 3-C 3Hs )]

(iii) Proton abstraction from the monoolefinic complex: Proton removal from an olefinic complex
can lead to the 113-functional moiety (i.e. monoolefin - H+ ~ allyl).
2PdCI 2 + 2 0 (i.e., CSH10 ) --
(cyclohexene)
ry
O':-Pd/CI"Pd~O"·
ra
,,/ '
ib
CI
[Pd 2CI 2(C sHg)2]
yl
m
he
lc
ea
th
e/
t.m
Note: Coordinated allyl ligands may be converted into the olefinic ligand by the addition of a
nucleophile to the coordinated allyl ligand.
e
(iv) Protonation of the diene complexes:

er
H
~ Fe(COh + HCI04 - (OChFe ~ CIO;

k
lic
Me
C
It is suggested that first H+ ion oxidises the metal centre to produce the metal-hydride bond
followed by the H- transfer to the coordinated butadiene. It may be compared with the addition
of H+ and electrophile E+ to [Fe(115-Cp)2], (Sec. 10.12.7).
c
CFe(COh-
0 H'
(1l4_ coordination)
(1l3_ coordination)
E
,,-
:.~ Fe(C% -
HCI
[EJ ]
"
:..- . . Fe(COh +cr- ~ [)'
:-Fe (COb O
'"
Me
II ]
ry
Here, at the first step, oxidative addition of H+ as H- causes the two electron oxidation of the metal
ra
centre. Then H- transfer occurs to 114-butadiene.
Note: The 11 4-butadiene and 113-methylallyl complexes are interconvertible, butadiene + H- ~
ib
methyallyl-
yl
~~-
m
~ CH -CH===CH-CH
C D CH-CH===CH 2 2 3
he
The required H- may be supplied from the M-H bond.
hv lc
-----I,... (115- Cp)Fe(CO)
-eo I
ea
~ CH 3
th
H- may be supplied by a solvent like THF.

e/
t.m
e
er
Pentadienyl Group
H
CH 2=CH-CH=CH-CH2 group, i.e. C5H 7 group. If it is taken as the C5H 7-radical, then
115-C5H7 can act as a 5e donor ligand. If it is treated as C5H7- (anion), then 11 5-C 5H 7 can act as a
k
6e donor ligand. However, it can function also as 11 1, 11 3 and 11 5 depending on the condition.
lic
[Fe(C 5H7)2] is called open ferrocene. Allyl and pentadienyl groups are generally described as the
enyl ligands.
C
In [Fe(CO)3(C 5H s)], 1, 3-pentadiene (C 5H s) binds like a butadiene (114-coordination, 4e donor)

but the complex can be oxidised to a 11 5-pentadienyl complex.
l]4-b~~di~ne~pe (............ Ph3C+BF4- [Ce(COl:J ]~F-

~~~~p;~:~~;n/(C5H8)~Fe(CO)3 -(_~P-h3-CH"';')---i"'· C 4
CH 11 5 -pentadienyl
3
complex
A similar reaction (i. e. addition of P-) is given below.
~~(COb ~
__C_s+_F_------:.. Cs+
F::f-!:vF
F0--\~Fe(COb
ry
F F F
ra
(11 4-cyclohexadiene
type coordination) (113_coordination)
ib
yl
9.20 COMPLEXES OF CYCLIC POLYENES: CARBOCYCLIC PI-COMPLEXES
m
9.20.1 Common Examples of Carbocycles with n-Electrons
The common carbocycles known to form complexes are:
he
lc
M7~
ea
Y)4_C 4 Ht- Y)s-CsH s Y)6_C 6H6
y) 4-eyclobutadiene
th
i.e., Y)6-benzene
dianion 11s-Cp-
e/
y) 5-eyclopentadienyl
"..--------.. . .v )
t.m
(Se)
oM
e
@ 0
er
I I
\ I
H
Cycloheptatrienyl Y)6_C 7Ha

Cycloheptatriene
or tropylium cation 116_cycloheptatriene
(C 7Ha)
k
117-C7H/
\. )
lic
V"
OM (Se) M
C
,'-;X
0 , , (cyclooctatetraene
I ,
I 2- I
I , \
,I dianion)
\ I
"
118-CaH~-
Cyclooctatetraene (cot) 116-eaHa
i.e., 11a-cot 2-
(CaH a) i.e., Y)6-cot
(10e)
(Se)
Obviously, the carbocycles satisfying the Huckel's rule of aromaticity (i.e. 4n + 2n-electrons) have
got an additional stability.
The n-MOs of the carbocycles, i.e. cyclic polyenes participate in making the interaction with the
metal orbitals. The filled n-MOs are used for donation of electrons to the metal centre and the vacant
n* -MOs are used for acceptance of electrons from the metal centre. The number of n-MOs is given by
the number of p-orbitals available for the n-MO formation. In these cyclic polyenes, each C-atom
provides one Pn-orbital. The relative positions of the n-MOs simply can be represented as in
Fig. 9.20.1.1.
ry
ra
>.
C')
ib
CD
c::
w
yl
Bary Centre
m
he
lc
ea
Fig. 9.20.1.1 Position of the n-MOs in cyclic polyenes.
The characteristic features of the n-MOs are given below:

th
(i) Number of n-MOs is the number of C-atoms, each providing one Pn-orbital.
(ii) Lowest n-MO which is fully bonding (no node); the next higher set (1 node); the next higher set
e/
(2 node), and so on.

(iii) If the number of C-atoms is odd, the highest set (fully antibonding) is doubly degenerate; if the
t.m
number is even, the highest set is nondegenerate.

(iv) Nodeless n-MO is of a-type symmetry; one nodaln-MO is of n-type symmetry; double nodaln-
MO is of cS-type symmetry.
e
Here it may be mentioned that all the n-electrons of a particular carbocycle may not participate in
er
metal coordination. For example, Cp- can function as 111-Cp- (2e donor), 113-Cp- (4e donor, i.e. one
double bond is kept out of coordination, binding as in 113-allyl), l1s-Cp- (6e donor) (cf Fig. 9.20.3.1).
H
Similarly, cot (CgHg) can act as 112_CgHg (2e donor, i.e. one double bond coordinates), 114_CgHg (4e-
donor, i.e. 2 double bonds coordinate as in 114-butadiene), 116_CgHg (6e donor, i.e. 3 double bonds
k
participate in coordination), l1g-CgHg (8e-donor, i.e. all the 4 double bonds coordinate) (cf Fig. 9.20.6.1).
lic
In the same way other carbocycles may also show the variable heptacity.
Here it may be mentioned that in the carbocycles, the n-bonding electron cloud is donated to the
C
metal centre and in the vacant n* -MOs, the metal electrons can be back donated. Thus, they can
function as the typical 1t-acid ligands.
Electron count: Sometimes the odd carbocyclic n-systems attain the stability of aromaticity (i.e. 4n
+ 2 n-electrons) by bearing a charge. For example, C SH6 (cyclopentadiene) attains the aromaticity (i.e.
61t electrons) in CsHs-. In the complex, M(Cp), the ligand Cp may be treated as a cyclopentadienyl
radical (-CsHs) or a cyclopentadienyl anion (i.e. CsHs-). Thus the oxidation states of the metal centre
may be described as:
[ MO(CsH s )] [M+1(CSH S)]

(Se-donor) (6e-donor)
i.e.,~
(Se-donor)
'O~~ C-O ~ 0- ~
ry
i.e.,
ra
U (5e-donor)
ib
yl
In terms of total electron count, it makes no difference whether Cp is treated as a 5e donor or as
a 6e donor ligand provided the appropriate oxidation state of the metal centre is assigned. Thus,
m
in both [Feo(C sHs)2] and [Fe II (C sHs)2], 18e configuration is attained. In the same way, allyl and
pentadienyl ligands may be considered as follows:
he
C3Hs- (4e donor) or ·C 3Hs (3e donor)
CSH7 i.e. CH2=CH-CH=CH-CH2- (6e donor)
·CSH7 i.e. CH 2=CH-CH=CH-CH2• (5e donor)
lc
ea
9.20.2 Cyclobutadiene Complexes
Cyclobutadiene (C4 H4 ) bearing 4 1t-electrons is antiaromatic and it is unstable. In C4 H4 , the four
th
p1t-orbitals generate 4 1t-MOs : \Ill' \112' \113 and \114 where \112 and \113 are degenerate. The electronic
e/
OC co co
,,1/
t.m
Fe
e
er
x0
4
H
~
k
z
lic
C
'V1 (0 nodal plane) 'V2 (1 nodal plane) 'V3 (1 nodal plane) 'V4 (2 nodal planes)
'V2PJC 1 ) + 'V2Pz(C 2) 'V2Pz(C 1) ± 'V2Pz(C2) ± 'V2PJC 1 ) - 'V2Pz(C 2) 'V2p (C 1 ) - 'V2Pz(C 2)
+ 'V2P z(C 3 ) + 'V2Pz(C 4 ) - 'V2PJC 3) ± 'V2Pz(C 4 ) ± 'V2Pz(C 3) + 'V2Pz(C 4 ) + 'V2~z(C3) - 'V2Pz(C 4 )
Matching
metal orbitals:
Fig. 9.20.2.1 n-MOs of cyclobutadiene and suitable metal orbitals matching for overlap interaction.
configuration is: \JII 2 (\JI2' \JI3)2. However, the detailed and finer analysis show the electronic configura-
tion as \Ill \IIf. Through the metal coordination, this electronic configuration may be changed and C4 H4
may be stabilised in the complexes.
[Note: If the vertical nodal plane of a MO passes through an atom then the AO (Le. atomic orbital)
of the atom will not participate in the construction of the MO. It happens so for \112 of allyl ligand (Fig.
9.10.1.1).]
ry
In the dianion, C4H42- i.e. cyclobutadiene2-, the 6 1t-electrons are distributed as: \111 2(\112' \113)4 and it
is aromatic (i.e. 4n + 2 1t-electrons, n = 1). The electron count depends on the consideration of the
ra
oxidation state of the metal centre:
[Mo(11 4-C 4H 4)] (4e-donor), [MII(114-C4H4)] (6e-donor)
ib
The prediction of stabilisation of the C4H4 moiety through complexation was made by H.C.
yl
Longuet-Higgins and L.E. Orgel in 1956 and it was realised within 3 years in the following reaction.
Mg:
m
A A
Efri-r
R R CI
he
2[Ni(CO)41 + -aco. R R
R
(R=Me)
R R lc RCI-r~
ea
CI A A
Dehalogenation of dihalocyclobutene leads to aromatisation. By using the same principle,

unsubstituted cyclobutadiene-complex has also been prepared.
th
q.~1
e/
+ [Fe 2(CO)g] - - - i• •
[Qj-Fe(CO)3 + FeCI 2 + 6CO
t.m
CI i.e., [(rt-C4H4)Fe(COhl
(dihalocyclobutene)
e
Cyclodimerisation of alkyne may lead to cyclobutadiene which is stabilised in a complex.

er
PhC===CP~ R~
H
[(rf -Cp)Co(PPh 3)21 CO(11 5-CP), R = Ph

k
A A
lic
Here many other polymerised products have been identified.

C
_Ph_C_ _ C_P~h Ph~CO(115_CP)

•• i.e.,
Ph
~ Co
Ph
Ph Ph
cod = cis, cis-cycloocta-1, 5-diene

Ph Ph
(a sandwich type compound)
Free cyclobutadiene is very much unstable due to its antiaromatic character but it can be trapped in
a Dies-Alder reaction with a suitable alkyne. It is illustrated in the following reaction where the C4H4
is released from [(OC)3Fe(1l4-C4H4)] through the oxidation by Ce(IV).
0]
R
ry
2 RC_CR
Ce(IV) • Fe + + 3CO + [ ~
ra
R
ib
Dewar-benzene type
yl
bicyclic product.
m
We have already mentioned that in the complex, [M(1l4-C 4H4)], the ligand may be considered as a
he
4e donor ligand (when 0 oxidation state is assigned to the metal centre) or as a 6e donor ligand
(when +2 oxidation state is assigned to the metal). However, at least, in some cases, electrophilic
substitution on the coordinated C 4H4 suggests the presence of C4H~- (i.e. aromatic dianion). One such
lc
example is:
ea
th
CH3-~-CI
e/
[Gj--Fe(CO)3 + + HCI
t.m
(Friedle-Crafts
reaction)
Note: [BH 2] group is isoelectronic with [CH] group. Thus the metalloborane clusters like
e
[Fe(CO)3(B 4H g)], [Co(lls-C sHs)(B 4H g)] are isoelectronic with their respective cyclobutadiene adducts
er
[Fe(CO)3(1l4-C 4H4)] and [Co(lls-C sHs)(1l4-C 4H4)].

H
9.20.3 Cyclopentadienyl Complexes

Accidental discovery (1950s) of [Fe(lls-C sHs)2], i.e. [Fe(lls-Cp)2] (called ferrocene) in a reaction
k
between FeC1 2 and CsHsMgBr is a milestone of organometallic·chemistry.

lic
FeCl 2 + 2CpMgBr ~ [ Fe (Cp)2] + MgCl 2 + MgBr2

C
Ferrocene was also isolated in a failed attempt.
N 2 -atmosphere [ ( ) ]
C sH 6 + Fe-dust------4) Fe Cp 2
The history (scientific serendipity) behind these accidental discoveries has been discussed in
Sec. 9.1.3
CsHs, CSH6 and C SH7 moieties can coordinate in different possible modes (cf. Fig. 9.20.3.1).
0-1-0
ry
ra
[Fe(CO)(l1 s-Cp)(1,3-1l 3-
cycloheptatrienyl) J
ib
yl
H>O
m
:-:"-Fe(CO)2(PPh 3 )
H ,.
he
(1l4-C sH s) (11 4 - CsHs)
[Fe(CO)2(1l4- C sH s)(PPh 3 )] [MO(CO)4(11 4- CsH s)]
lc
ea
~
th
e/
Ni
H
t.m
H
( ...
H
H H
e
[N i(llS-CsH s)(1l3-G sH 7 )] [Re(CO )2( lls-GsH s)(llLCsH s)]

er
Fig. 9.20.3.1 Different modes of coordination by CsH s, CSH6 and C SH7 .

H
(A) Bonding in Ferrocene or Metallocene [M(Cp)2l (in general): Five C-atoms of CsH s ring
provide five p-orbitals to construct the 51t-MOs.
k
Energy order: 'VI (no nodal plane) <'Vb 'V3 (one nodal plane perpendicular to the ring) <'V4' 'Vs (two
lic
nodal planes pendicular to the ring).

'Vt (bonding MO) is of at symmetry.
C
'V2' 'V3 (weakly bonding MOs) are of el symmetry

'V4' 'Vs (antibonding MOs) are of e2 symmetry
The 1t-MOs of the CsHs-ring are shown in Fig. 9.20.3.2. In the construction of the 1t-MOs, it is to be
remembered that a vertical nodal plane must satisfy the following conditions:
i.t must pass through the centre of the ring; when it passes through a nucleus, the AO of the atom
will not participate in the construction of the MO.
Now for the construction of the MOs of [Fe(Cp)2]' we are to construct the ligand group orbitals
(LGOs) by using the It-MOs of the two CsHs-rings. These LGOs will combine with the suitable metal
orbitals to construct the MOs of ferrocene.
\Vs
ry
8 1 : antibonding
ra
ib
yl
m
he
~
~
Q)
c
W lc
ea
81 : weakly bonding
th
e/
t.m
e
\V 1 81: strongly bonding

er
H
k
Fig. 9.20.3.2 Pi-molecular orbitals of the CsH s ring, nodal planes pass through the dotted lines.
lic
'1'1 : 'I' 2pz (C 1 ) + 'I' 2pz (C 2 ) + 'I' 2pz (C 3 ) + 'I' 2pz (C 4 ) + 'I' 2pz (C s )
C
'I' 2 : 'I' 2pz (C 1 ) + 'I' 2pz (C 2 ) ± 'I' 2pz (C 3 ) - 'I' 2pz (C 4 ) - 'I' 2pz (C s )
'I' 3 : 'o/2pz (C 1 ) - 'I' 2pz (C 2 ) - 'I' 2pz (C 3 ) - 'I' 2pz (C 4 ) + 'I' 2pz (C s )
'I' 4 : -'I' 2pz (C 1 ) + 'I' 2pz (C 2 ) ± 'I' 2pz (C 3 ) - 'I' 2pz (C 4 ) + 'I' 2pz (C s )
'l's : -'I' 2pz (C 1 ) + 'I' 2pz (C 2 ) - 'I' 2pz (C 3 ) + 'I' 2pz (C 4 ) - 'I' 2pz (C s )
By considering the staggered positions of the CsHs-rings in [Fe(Cp)2] (i.e. in D 5d symmetry),
formation of the LOOs is illustrated in Table 9.20.3.1 and Fig. 9.20.3.3.
Table 9.20.3.1 Formation of LGOs in [M(Cphl (staggered condition, D Sd symmetry and suitable metal
orbitals for overlap with the LGOs)
Combination of n-MOs of two Symmetry of Appropriate Fe-orbitals,

staggered Cp-rings of LGOs matching with the LGO (type of
interaction with the LGO)
ry
4p: (a-type)
{ 'til + 'til G211
ra
'til - 'til GIg 4s, 3d _2 (a-type)
{ 4P." (n-type)
ib
'tI2 + 'tI2 el u
'tI2 - 'tI2 el g 3d.": (n-type)
yl
{ 'tI3 + 'tI3 el u 4px (n-type)
m
'tI3 - 'tI3 el g 3dx: (n-type)
he
{ 'tI4 + 'tI4
'tI4 - 'tI4
e2u
e2g
lc
No suitable metal orbital
3dx." (8-type)
ea
{ 'tis + 'tis
'tis - 'tis
e2u
e2g
3dx2 _./ (8-type)
th
It is evident that the '+ combination' of the n-MOs of the Cp-rings gives the ungerade (u) symmetry
e/
while the '- combination' gives the gerade (g) symmetry; the e2u LGOs remain as the nonbonding ones
in the MO diagram of [Fe(Cp)2J.
t.m
LGO Suitable metal orbitals matching with the LGO

e
er
H
k
z
lic
C
----~ Y (for a-type interaction)
x
pz
ORGANOMETALLICS AND METAL CARBONYLS: n-AclD METAL COMPLEXES 1467
z z
ry
1----. Y It.A~}----''' Y
ra
s
ib
x x
(for a-type interaction)
yl
m
he
z
lc
ea
th
e/
x
t.m
(for IT-type interaction)

e
er
H
z
k
lic
C
~
I ----~~----. y
~
(IT-type interaction)
ry
ra
~---~y
ib
x
yl
(for 1t-type interaction)
m
he
lc
ea
z
th
e/
-;
I
t.m
-;
x
(for 1t-type interaction)
e
er
H
k
lic
C
+ No suitable metal orbital

(nonbonding)
-;
ry
I
-;
ra
x (for 8-type interaction)
ib
yl
m
he
lc
ea
(nonbonding)
th
e/
t.m
e
er
z
H
k
y
lic
x
C
(for 8-type interaction)
(e 29 )
Fig. 9.20.3.3 Schematic representation of formation of the LOOs through the combination of n-MOs of two staggered
Cp-rings (D Sd symmetry) and suitable metal orbitals for overlap with the LOOs. (For the sake of simplicity '+' and '-'
signs of the lobes are not shown; however lobes of same sign are indicated with shade and lobes of opposite sign are
indicated without any shade).
The approximate MO-energy level diagram for [M(CP)2] (in general, M stands for a transition metal)
is shown in Fig. 9.20.3.4.
ry
ra
ib
yl
m
he
lc
ea
th
Main contributing
e/
interaction: e1g (d xz ' dyz)

a2u (pz)
t.m
TASOs i.e. MOsof AOs of the metal

LGOs for 2 Cp [M(Cp)2l
rings
e
Fig. 9.20.3.4 Approximate MO energy diagram of the staggered metallocene [M(CphJ. N.B. Electron distribution in the
er
MOs for ferrocene [Fe(CphJ.
(B) Characteristic features of the MO energy level diagram of [M(CP)2]: Here it is important to
H
mention that when the population density of electron in the (n - l)d level is sufficiently high, the energy
order is:
k
np)ns)(n-l)d
lic
(i) The al g LGO can interact (a-type) with the metal4s and 3d 2 orbitals but the said metal orbitals
z
C
are of much higher energy compared to that of the LGO. Between the 4s and 3dz2 orbitals, the
4s orbital is still of higher energy. Thus the following interaction gives the three resultant sigma
MOs.
alg{LGO) + 4s{M) + 3dz2 {M)
1 CJ-type
Three MOs i.e. afg (a-BMO), a~: (a-NBMO) and a~g (a-ABMO).
The BMO (al~) is predominantly enriched with the character of the al g LGO. However, this is the
lowest a-HMO. The NBMO (al~b) is basically the metal 3dz2 orbital while the ABMO (al;) is
predominantly enriched with the character of metal 4s orbital.
(ii) The a2u LGO can interact (a-type) with the metal 4pz orbital to produce two a-MOs.
a2u(LGO) + 4pimetal) (a-type») two MOs, i.e. a~u (cr-BMO) and a2:(a-ABMO)
ry
But the energy difference between the a2u(LGO) and metal4pz orbital is very high. Consequently,
the BMO (a~u) is basically the corresponding LGO while the ABMO (a;u) is basically the metal
ra
4pz orbital.
(iii) By considering the energy matching factor, the interaction (n-type) of two el g LGOs with the
ib
metal 3dxz and 3dyz orbitals is very strong. This interaction produces two 1t-MBOs and two
yl
ABMOs.
m
Two e1g(LGOs) + 3dxz (M) + 3dyz (M)
he
lit-interaction
Two efg (cr-BMOs) + Twoe: g (cr-ABMOs)lc

ea
These two strongly HMOs, i.e. e~g play the most crucial role to stabilise [M(Cp)2l. The e~g
MOs are predominantly enriched with the character of the metal dxz and dyz orbitals.
th
(iv) The two el u LOOs can interact (n-type) with the metal 4px and 4py orbitals to generate 4n-MOs.
Because of the significant energy difference, the 2 BMOs are close to the LOOs while the 2
e/
ABMOs are close to the metal orbitals.
) T woe 1u 1t-BM0 s) + Two e1u

* (1t-ABM0 s )
t.m
) + 4px' 4py ( M ) 1t-interaction b (

Two e1u (
LOOs
(v) ~e two e2g LGOs can interact (8 type) with the metal3dxy and 3dX2 _y2 orbitals to produce the two
8-BMOs (e~g) and two 8-ABMOs (e;g).
e
er
Two e2 g(LGOs) + 3dxy (M) + 3dX2 _y2 (M)

H
lO-interaction
k
Two e~g (b-BMOs) + Twoe;g (b-ABMOs)

lic
Compared to the e2g LOOs, the corresponding metal d-orbitals are of much lower energy. Conse-
C
quently, e~ BMOs are basically the metal 3dx2 _y2 and 3dxy orbitals while the e;g ABMOs are
basically the corresponding LOps.

(vi) For the two e2u LOOs, there is no metal orbital of appropriate symmetry to interact. This is why,
these LGOs remain as the nonbonding ones.
Most important bonding interaction in [M(Tl 5-Cp)2]

Pi-interaction by the metal dxz and d vz orbitals with the appropriate n-MOs of the Cp-rings leading
to the highly stable el g BMO.
From the MO-energy level diagram, it is evident that the number of BMOs and NBMOs is nine in
which 18e can be accommodated. If the number of valence electron is more than 18, then the additional
electron will be placed in the higher ABMO to destabilise the system.
Electronic configurations of some metallocenes [M(Cp)2] of the 1st transition series are given in
Table 9.20.3.2.
ry
Table 9.20.3.2 Electronic configurations of [M(1l5-Cp)2], i.e. [M(CP)2] of some I st transition series (cf Fig.
9.20.3.4).
ra
[M(Cp)J Total valence Electronic Number of Colour Melting
ib
electron count* Configuration unpaired electron point
yl
[V(Cph] 3 + 2 x 6 = 15 (afg)2 (afu)2 (efg)4 (efu)4 3 Purple -168°C
(Vanadocene) (efg)2 (at:)1 (J.! = 3.84 B.M.)
m
[Cr(Cph] 4+2x6=16 (afg)2 (afu)2 (efg)4 (efu)4 2 Scarlet -172°C
(efg? (al~b)1
he
(Chromocene) (J.! = 3.20 B.M.)**
[Mn(Cph] 5+2x6=17 (afg)2 (a{u)2 (efg)4 (efu)4 5 Dark
(Manganocene) (efg)2 (ar;)1 (e;g)2 (J.! = 5.86 B.M.) brown -173°C
[Fe(Cph] 6+2x6=18 (afg)2 (a{u)2 (efg)4
lc 0 Orange -173°C
ea
(Ferrocene) (efJ4 (e£)4 (ar;)2
[Co(Cph] 7 + 2 x 6 = 19 (afgf (afu)2 (efg)4 (efu)4 1 Purple -173°C
th
(Cobaltocene) (efg)4 (ar%)2 (e;g)1 (J.! = 1.73 B.M.)

[Ni(Cph] 8 + 2 x 6 = 20 (afg)2 (afu)2 (efg)4 (efu)4 2 Deep green -173°C
e/
(Nickelocene) (efg)4 (ar;f (etg)2 (J.! = 2.86 B.M.)

t.m
* If [M(Cphl is considered as [Mo(Cphl, then the Cp-ring can act as a 5e-donor ligand. If it is considered as
[MII(Cp-hJ, then the Cp-ring acts as a 6e-donor ligand. **J..lobs ) J..lspin = 2.8 B.M.
(C) Properties of the metallocenes in terms of the MO energy diagram:

e
(i) Explanation of the 18e rule in metallocenes: It has been already mentioned that all the bonding
er
and nonbonding MOs can be filled in by placing 18 electrons. It explains the 18e rule for stability
of the metallocenes. It is attained in [Fe(Cp)2] and it is quite stable. However, there are many quite
H
stable metallocenes failing to satisfy the 18e rule.

(ii) Violation of the 18e rule in fairly stable metallocenes: [V(CP)2] (15e), [Cr(Cp)2] (16e), [Mn(Cp)2]
k
(17e), [CO(CP)2] (1ge), [Ni(Cp)2] (20e) without maintaining the 18e rule are also fairly stable. It
lic
can be explained by considering the charater of the efg al~ and e~gMOs. The efg is only weakly
bonding and these are basically the metal d x2 -i and dxy orbitals. Similarly, the e;g MO is only
C
weakly antibonding and these are mainly enriched with the metal d.t:' d vz orbitals. Thus, electrons
present in these MOs, i.e. e2%, al'; and e~g do not have much control on the stabi~ity of the
metallocenes.
This is why, the metalloctfnes of 15e, 16e and 17e configurations possess some vacancies in the
e2~ and al;h MOs. The absence of electrons in such nonbonding or weakly bonding MOs does not
create any remarkable loss of stability. Similarly, placement of one and two electron(s) in
the weakly antibonding el; orbital for the 1ge and 20e cofigurations does not destabilise the
system significantly. Placement of electrons in these weakly antibonding MOs slightly elongates
the M-C bond distance.
[ Fe(Cp)2](18e) [ Co(Cp)2](1ge) [Ni (Cp)2 ](20e)

M-C (pm):' 206.5 212.0 219.7
Nickelocene readily reacts with PF 3 to give the 18e product.
[ No (11 -Cp)2] + 4PF3 ~[Ni(PF3)4J + Organic products.

5
ry
(20e) (18e)
ra
Ferrocene (18e) is unreactive toward 12, But, [CO(CP)2] (1ge) is readily oxidised to cobalticinium
ion, [CO(CP)2]+ (18e) to attain the 18e configuration.
ib
2[Co (11 5 -Cp)2] + 12 ~2[Co(11 5 -Cp)2r + 2r
yl
(1ge) (18e)
m
(iii) Tendency of metallocenes (lacking in 18e configuration) to add ligands to adopt the bent
metallocene structure to attain the .18e configuration: In such cases, the electron deficient
he
metallocenes readily add ligands (through the oxidative addition) to give the product
[(1l5-Cp)2MLx] to attain the 18e configuration. In such cases, the Cp-rings are tilted back from
lc
their parallel positions. This changes the MO energy diagram. Tilting of the Cp-rings allows the
a'i% and efg (degenerate) orbitals to create three new MOs through their appropriate mixing. These
ea
3 MOs can accommodate 6 electrons. In this event, the lower 6 MOs (i.e. upto efJ remain more
or less unpurturbed. These 6 MOs accommodate 12 electrons and three new MOs can accommo-
th
date 6 electrons to give the 18e configuration. It happens so in the following examples:
e/
[(11 5 -Cp)2 Re - HJ, [(11 5-CP)2 MO ( : } [(11 5 -Cp)2Ti (CO)2 J,

t.m
~
@fRe-H
H", ~ OC'" ~ H", ~
/Ti"@ H/ '@
e
/MO H-Ta
H'@
er
OC
H
18e 18e 18e

\ )
'V"
k
Bent metallocenes
lic
Reactivity of molybdenocene towards the attainment of 18e configuration is reflected in the

C
following reactions.
Bent
metallocene
[Ti(1l5-Cp)2] (14e), i.e. titanocene is quite interesting. Now, it is established as a dimer having the
bent metallocene structure as expected for the electron deficient .!'1ctallocene. It nlay be;".not~d
'J
that [Ti(*Cp)2l i.e. [Ti(l1s-CsMes)2l can exist as a monomer. Probably the the bulky substituents
prevent the bent sandwich structure. The same thing happens for [Re(l1s-CsMes)2l
Dimeric form of titanocene (green) obtained from the

H reduction of [Ti(1l5-CP)2CI2]
TI~/I
'/~T'
ry
0JH@
ra
J.!-(1l5: 115-fulvalene)di-J.!-hydrido-bis(cyclopentadienyltitanium)
ib
(D) Magnetic properties of the metallocenes: Sometimes it becomes difficult to predict the magnetic
yl
properties in advance. To predict this property, we are to consider the pattern of electronic configuration
m
in the e2~' at; and el~ MOs (ef Fig. 9.20.3.5). These are mainly the metal orbitals.
he
(Weakly antibonding) e;g (dXZI dyz )
~2
lc
ea
a7~ (d/)
~1
th
(Weakly bonding)
, e2~ (d _l ' dxy)
2
e/
Fig. 9.20.3.5 Partial MO energy diagram for metallocenes [M(lls-Cphl i.e. [M(Cphl (cf Fig. 9.20.3.4).
t.m
In terms of Fig. 9.20.3.5, if ~I and ~2 ( P (pairing energy), then electron pairing in the e~g level will
not occur. It happens so for the M 2+ centres which are the early members of the 3d-series. For, [V(Cp)2]
and [Cr(Cp)2]' the electronic configurations are: (e~g)2 (anl~)1 (i.e. ~I ( P) and (e'2,{?)3 (ar;)1 (i.e. ~1 ( P
e
but ~l + ~2 ) P). For [Mn(Cp)2], the electronic co'"!f~guration is: (e'2g)2 (all,~) I (e;,{?)2 i.e. ~1 + ~2 ( P
er
(ef effect of exchange energy). It leads to a high spin complex.

For, [Cr(Cp)2]' ~1 + ~2) P while for [Mn(Cp)2], ~I + ~2 ( P can be partly rationalised in terms of
H
very high exchange energy in the d5 system and it favours the high-spin configuration. It is interesting
to consider the fact that [Re(Cp)2] (Re, a heavier congener of Mn) is believed to be a low..spin complex
k
having the configuration: (e2%)4 (al;h) I (i.e. ~I ) P) because of its higher crystal field splitting power.
lic
However, [Re(Cp)2] actually exists as [(Cp)2ReH] which is diamagnetic (18e configuration).

Now let us compare the magnetic properties of [Mn(l1s-CsHs)2], i.e. [Mn(Cp)2] and
C
[Mn(l1s-CsMes)], i.e. [Mn(Cp*)2l where Cp* denotes the pentamethyl eyelopentadienyl. Their elec-
tronic configurations are:
[Mn(Cp)2]: (e2%)2 (al;h)l (el;)2 i.e., ~l + ~2 ( P,fully high-spin state
[Mn(*Cp)2l: (e2%)4 (al;b)1 (el;), i.e. ~l + ~2 ) P, low-spin state.
The magnetic moment of [Mn(Cp)2] corresponds to 5 unpaired electrons while for [Mn(*Cp)2]' the
magnetic moment suggests 1 unpaired electron. The spin pairing in [Mn(*Cp)2] occurs due to the
higher crystal field splitting power of *Cp compared to that of Cp (i.e. unsubstituted one). The
electron pushing Me-groups of Cp* make it a better donor ligand and it makes the ligand a stronger field
ligand.
Here it is interesting to mention that [Mn(l1s-CsH4Me)2] shows an anomalous magnetic moment.

It indicates the presence of spin equilibrium.
[~n(~5~5115)2J [~n(~5~5114~e)2J [~n(~5~5~e5)2J

High-spin High-spin ~ low-spin Low-spin
ry
Crystal field splitting power increasing)
ra
For [Fe(Cp)2], [Co(Cp)2] and [Ni(Cp)2], the condition, L1j, L12 ) P leading to the low-spin complexes
can explain their magnetic properties.
ib
Note: Here it is important to note that for [Cr(Cp)2]' the J.lobs (= 3.20 B.M.) value is greater than the
J.!spin value (::::: 2.8 B.M.). It may be due to the contribution of the high spin state suggesting the existence
yl
of the spin state isomerism (ef exchange energy of the cr system is also fairly large).
m
(E) Dependence of Al and A2 (cj. Fig. 9.20.3.5) on d n configuration (ef Chapter 3, dependence of
10Dq on tf1 configuration): The above discussion indicates that the magnitudes of L1 1 and L1 2 depend on
he
the d n configuration for a particular oxidation state. In fact, the relative energies of (n - 1)d, ns and np'
orbitals depend on the extent of electron population density in the (n - l)d level and thus it controls the
lc
energy matching between the ligand LGOs and metal orbitals. This energy matching determines the
values of L1 1 and ~2'
ea
(F) Kinetic and thermodynamic stability of the metallocenes: For the 18e configuration, all the
bonding and nonbonding (i.e. weakly bonding) MOs are filled in giving rise to the electronic configu-
th
ration: (ef)4 (a'11~)2 (e;g)O (diamagnetic). The HOMO is al~ and LUMO is e~g. For ferrocene, i.e.
[Fe(Cp )2], this condition is attained. Here, no low energy vacant orbital is present and the
e/
HOMO - LUMO energy gap is sufficiently high. This provides the kinetic stability. Filling in the all
bonding and nonbonding (i.e. weakly bonding) MOs gives the thermodynamic stability in [Fe(Cp)2J.
t.m
For [Co(Cp)2] or [Ni(Cp)2], the electrons present in the ABMO may be easily lost. [Co(l1 s- Cp )2] is
readily oxidised to [Co( lls-Co)2]+ which is remarkably stable. It can even tolerate the attack of cone.
HN0 3 (ef ferrocene is readily oxidised to [Fe(l1s-Cp)2]+ by dil. HN0 3). Though both [Co(115-Cph]+
e
and [Fe(l1s-Cp)2] are isoelectronic, the oxidative stability of [Co(TlS-Cp )2]+ is more because it
contains Co(III) while ferrocene contains Fe(II). [Co(l1 S-Cp)2]+ (18e) reacts with H- to give a neutral
er
compound, [Co(115-Cp)(114-C5H6)] (18e). At low temperature, [CO(CP)2] is oxidised to an unusual

orange coloured product.
H
QH
k
CIX0-)(;)1-
lic
-
O2 (air) 1 H- I
C
~ ~ ; [CO(~5_Cp)2j+ _ ~
The electron deficient metallocenes, e.g. [Ti(Cp)2]' [V(CP)2]' [Cr(Cp)2]' etc. to attain the 18 elec-
tron configuration, easily add to the ligand (L) to produce [M(CP)2(L)x] which adopt the bent metallocene
structure.
Among the metallocenes of 1st transion series,!errocene is only air stable and the stability sequence is:
Stability sequence of [!\tl( Cp )2]: Ni) Co ) V » Cr
s
Generally, [M(*Cphl i.e. [ M(11 s--C Me S S)2 J, is less reactive than [M(Cphl i.e. [ M(11 --CsH s )2J,
because in [M(*CP)2]' there is a protection from the steric crowding. The C-H bonds are substituted
by the C-Me bonds in *Cp. This also provides the kinetic stability.
(G) Cp-rings in other systems: Indenyl, azulene, coupled rings as in fulvalenes, etc. may provide
the Cp-ring for complexation.
ry
Of> ~ H
ra
ib
yl
(OCbFe--Fe(CO)2 (OC)2Ru RU(CO)2
M n(COb
m
(Indenyl group) [(11 3 , l1s-C10Ha)Fe2(CO)S] (Fulvalene like system)
(Azulene system)
he
lc
ea
th
e/
bis(fulvalene)diiron, i.e. 1, 1'-biferrocenyl, [Fe2(C1oHahl

t.m
(H) Structural features of [M(115-Cp)2]: In ferrocene, the planar Cp-rings are in parallel planes to
give the sandwich structure. In ferrocene, all the C-C distances are almost equal (-140 pm). Similarly,
.all the Fe-C distances are equal. This is why, it is reasonable to conclude that here the Cp-rings bind
as the 115-rings.
e
er
H
k
lic
C
Staggered [Fe(Cp)2] Eclipsed [Fe(Cp)2] Eclipsed [RU(Cp)2] Eclipsed [OS(Cp)2]

(in crystal) gas phase (in crystal) (in crystal)
Fig. 9.20.3.6 Sandwich structures of some representative metallocenes like ferrocene, ruthenocene and osmocene
Eclipsed configuration ~ Pentagonal prism (DSh )
Staggered configuration ~ Pentagonal antiprism (D Sd )
Distance between the paraflel planes of the Cp-rings of ferrocene is about 325 pm. Relative orien-
tation of the Cp-rings of ferrocene depends on the physical state. In solid state, the Cp-rings are
arranged in a staggered configuration tn give the D Sd symmetry while in the gas phase, the Cp-rings
are in an eclipsed configuration to attain the D Sh symmetry. Finer structural analysis shows that even
in solid state, ferrocene adopts a nearly eclipsed configuration (rotational angle between the rings:::: gO).
All these observations indicate that the energy difference between the eclipsed (OSh) and staggered
(D Sd ) configurations is not very high and the rotational energy barrier (i. e. kinetic barrier) of the Cp-
rings is not also high. It has been estimated that in ferrocene, the rotational energy barrier of the rings
in ferrocene in gas phase is about 4-5 kJ mol- 1 and energy difference between the two configurations
ry
is comparable in magnitude to the intermolecular forces in the solid state. Thus, preference to the
staggered configuration in solid state of ferrocene is due to the crystal packing forces.
ra
Here it may be mentioned that ruthenocene, i.e. [Ru(llS-Cp)2] and osmocene, i.e. [Os(lls-Cp)2] (ef
Ru and Os are the heavier congeners of iron) adopt the eclipsed configuration in solid state.
ib
yl
m
he
lc
ea
th
Fig. 9.20.3.7 Sandwich structures of some metallocenes involving (1l5-CP) ring and other carbocycles.
(I) Reactivity of the cyclopentadienyl rings of ferrocene: This aspect has been discussed in detail
e/
in Sec. 10.12.7.
t.m
(J) Fluxional behaviour of the coordinated cyclopentadienyl rings: This aspect has been dis-
cussed in detail in Sec. 10.11.3.
(K) Bent metallocenes: In [M(llS-Cp)2] i.e. [M(CP)2]' generally the Cp-rings are in parallel planes
to give the sandwich structure. But in the bent metallocenes [(Cp)2MLx] e.g. [CP2ReH], [Cp2Mo(H)2],
e
[CP2TiL 2] (L = CI, CO), [CP2TaH 3], etc., the Cp-rings are tilted with respect to another. It happens so
er
due to the accommodation of the additional ligands added to provide the 18e configuration. Thus it
happens so when [M(Cp)2] is electron deficient (i.e. 18e configuration is not attained). In fact, in such
H
cases, the MO-Ievels are modified. This aspect has been already discussed.
(L) Coordinating behaviour of the CsHs, CSH6 and CSH 7 rings: These are illustrated in Fig.
k
9.20.3.1. If lls-Cp is considered to act as a 6e donor ligand then the lll-Cp ring is considered to act as
lic
a 2e-donor ligand. The intermediate situation, i.e. 113-CP will function as the 113-all y l group to act as
a 4e donor ligand. The gradual transformation, lls-Cp ~ 113-Cp ~ 1l1_Cp (called haptotropic shift)
C
leads to the addition of the 2e-donor ligands successively, i.e.
@-M : L
. G-M(L) +L
:II ()LH
~ M(L)2
(1l5_Cp) (1l3_Cp) (1l1-Cp)
(Haptotropic shift)
The 113-Cp mode is itself very unstable however it can be stabilised in the indenyl complexes where
the 113-Cp ring is stabilised by the fused aromatic benzene ring.
When the Cp-ring coordinates in the modes like T)3_Cp or T) I_Cp (i.e. other than the T)s-Cp mode), the
system is described as slipped ring system. The above concept is experimentally verified in the
ry
[Re(T)s-Cp)(Me)(NO)(PMe3)] ·complex.
ra
[ Re(lls-ep)(Me)(NO)(PMe 3)] < +PMeJ \ [ Re(1l3-ep)(Me)(NO)(PMe 3)2]
ib
1 +PMe,
yl
m
s
CsH + [Re(Me)(NO)(PMe 3 )4r (+PME I [Re(1l'-ep)(Me)(NO)(PMe 3)3]
he
+PMe3 3 +PMe 3 1 +PMe 3 0
i.e., T) 5 ~,=====\T) , 'T) , 'T)
lc
Helerocycles related to the CsH s ring and their complexes
ea
[(OC)3Mn(T)s-C4H4N)], [(OC)3Cr(T)s-C4H4S)], [(T)s-C sH s)Fe(T)s-C 4H 4N)] (azaferrocene),
[(T)s-CsH s)Fe(T)s-C4H 4P)] etc.
th
(M) Examples of mixed ligand complexes involving the Cp-ring as a ligand: The Cp-ring may
e/
coordinate in different ways such as T)s-Cp, T)3_Cp and T) I_Cp. These are illustrated in different mixed
t.m
ligand complexes (Fig. 9.20.3.1) and some examples are given below.
~~ @-V(COl4 @-Mn(COl3 @--Mo(COl3CI

e
~T1~ [(tf-Cpl2T1(COl~,
er
@--Co(COl2 @--Ni(l'.Ol, [(lls--epl2Mo(COl]

H
m(11 1-Gp)2(115-Gp)2]
k
)[(11 5- CP)2 CO (CO)2]; [CO(115_CP)2J~[(115_CP)2CO(CO)2J

lic
o
C
co /;~
@-Rt-CO
f{jNi Ni?g
Q H
[Re(CO)2(11 5-Cp) (11 2-C s H6 )]
H
(OC)2MO -()<HH
[Mo(COh(11 4-e sHs)]
ry
OC OC g I(}
ra
[Fe(CO)sl CsH
s
• (OChM- .', -0<- HH -eO ..
- OC-"'MO @ ---- ------- "'M/"'M~
~
g
ib
or [RU3(CO)12) / '/ "
H ~ 'CO
yl
m
he
lc
ea
(L=CO)
[Mo2(CO)s(l1 S- Cp)2]
Fig. 9.20.3.8 Coordinating behaviour of C 5 H5, C5H6

th
(N) Triple deckers cyclopentadienyl complexes: In such cases, three layers of Cp-rings are stacked
e/
in parallel planes and metal-centres are sandwiched by such layers. [Ni 2(llS-Cp )3]+ is an example of this
group. Here, the middle Cp-ring acts as a bridging ring. Similarly, in [Co2(1l6-C6H6)(l1S-Cp)2], the
t.m
benzene ring acts as a bridging ligand and in [Co2(l1S-Cp)2(l1s-CsHs)]2+, the l1 s-e sHs ring bridges.
[@-Ni-@-Ni--@r
e
er
[@-co-@-co--@]
H
[@-co-@-co--@r+
k
lic
Fig. 9.20.3.9 Structures of some triple deckers sandwich complexes.

C
(0) Convalent vs. ionic bonding in the cyclopentadienyl complexes: The ionic compounds are
expected to undergo hydrolysis favourably because of the presence of free Cp- group.
NaCp + H 20 ~ NaOH + CSH6
MgCp2 + 2H 20 ~ Mg(OH)2 + 2C sH6
Ionic Compounds Mn(Cp)2 + 2H 20 ~ Mn(OH)2 + 2C sH 6
Ln(Cp)3 + 3H20 ~ Ln(OH)3 + 3CsH6
Ln represents the representative lanthanides like Sm.
Fe(Cp)2 + H 20 ~ No reaction
NaCp is fully ionic but Mg(CP)2 possesses both the ionic and covalent character. Thus from the ease
of hydrolysis, we can say only that the anionic character of the cyclopentadiene moiety is more.
(P) Synthesis of cyclopentadienyl complexes: Accidental discovery of ferrocene has been already
discussed. However it can be easily prepared in the following reaction.
2C sH6 + 2KOH + FeCl 2 ~
[Fe(Cp)2] + 2KCI + 2H 20.
Actually, CsHs- generated in situ reacts with Fe(II) to give ferrocene.
ry
CsH s- may also be in situ generated in presence of the organic base (R 3N). Fe(II) generated in situ
ra
from the metallic iron can react with CsHs- to give [Fe(Cp )2]' It is illustrated below.
Fe+2R 3 N+HCI- ~FeCI2 +2R 3 N +H 2
ib
FeCl 2 + 2C sH 6 + 2R 3 N ~ [ Fe (Cp)2] + 2R 3 N+HCI-
yl
m
he
NiCl 2 +2C sH 6 +2Et2NH~[Ni(Cp)2J + 2Et 2NH;CI-
Na+Cp- or TI+Cp- can be used to prepare the cyclopentadienyl complexes.
lc
MX2 + 2NaCp ~ 2NaX + [M(CP)2]
ea
MX 2 + 2TICp ~ 2TIX + [M(CP)2]
th
TiCl 4 + 2TICp~[ Ti(Cp)2C12 ] + 2TICI

e/
TIX being insoluble can be separated easily. NaCp is also highly reducing. In fact, there are some
advantages in using TICp over NaCp. This aspect has been discussed in Sec. 9.15.4.
t.m
NaCp and TICp are prepared as follows:
ex H
+ Na
THF
~ NaCp +
1
"2 H2
e
H
er
TI 2SO/KOH
CsH s ------:1~. TICp
H
Highly electropositive metals like Mg can directly react with C SH6 to release hydrogen.
Mg(s) + 2C sH6(g) ~ [Mg(Cp)2] + H 2
k
Sometimes, CSH6 can react with the metal salt in presence of an organic base (which abstracts proton
lic
from C SH6 ).
C
CoC1 2 + 2:B + 2C sH 6 THF) [CO(CP)2 ] + 2B+H + 2Cl-; (B=Et 2NH)

Molybdenocene can be prepared as follows:
MoCl s - -NaCp, NaBH

----+)
4 [()
Cp 2Mo (H) 2] 7';;;f { Mo(Cp)21
(red brown solid)
(Q) Synthesis of mixed ligand complexes having the Cp ring as a ligand: Some representative
examples are shown in Fig. 9.20.3.8.
(R) Cp as a ligand towards the main group elements: The representative examples like [M(CP)2]
(M = Be, Mg, Ca) and others are discussed in Sec. 9.15.
9.20.4 Arene Complexes: Benzene Complexes

Benzene and its substituted derivatives like 1, 3, 5-trimethyl benzene, (i.e. mesitylene), hexamethyl
benzene, can function as the 6e donor ligands. Such ligands are generally described as arenes (Ar).
The classical example, dibenezenechromium complex was prepared by F. Hein in 1919 but it was
not characterised until 1954. It was first prepared in the following route:
ry
PhMgBr (Grignar~ reagent) _ _
crC_l_~)[Cr(OEt2)3Ph3]' (mono-hapto Complex)
3
(in Et 2 0)
ra
1
ib
. [Cr (11 6 --e.., 6 H6 )2 ] (
yl
[Cr (C 6 H 6 )]
2 I.e.,
reduction
Na S2 0 4
2
(Dark-brown)
m
The 'general method to prepc;ue the arene complexes was developed by Fisher and Hafner (1955).
he
It is as follows: .
3CrCl3 + 2AI :+ AICl 3 + 6C6H6 ~ 3[Cr(C6H 6)2]+ [AICI4 ]-
lc
Al is used to reduce CrCl 3 and AICl 3 is used as a catalyst. The orange-yellow cation [Cr(C6H 6)2]+ can
be easily reduced by an aqueous solution of dithionite.
ea
[Cr(C 6H 6 )zr +~Szo~- +20H- ~[Cr(C6H6)z]+SO;-+HzO.
th
Metal vapour method: Condensation of metal atom vapour with benzene or its derivatives gives the
e/
bis-arenes.
M(g)+ C 6H 6 (g) [M(C 6 H6 )z]'<M = Cr, Mo).
t.m
CO,ndensation)
From the metal-carbonyls, substitution of 3CO groups by one arene leads to the arene complexes.
Ar+ [M(CO)6J~[M(T\6_Ar)(CO)3]+3CO, (M = Cr, Mo, W).

e
er
~
H
k
Cr
lic
C /1"" C
C
(
# C ~
o III 0
v o
Sandwich structures
Fig.9.20.4.1 Some representative examples of complexes having the Tl 6-C 6H 6 ligand.
Other examples of substitution are:

[Mn(CO)sCI] + C 6H6 + AICl 3 ~ [(1l6-C6H 6)Mn(CO)3]+ AIC1 4- + 2CO

Polymerisation of alkynes may lead to the arene complexes.
[Ph 3Cr(THF)3] Me-C==C-Me {(116-C6Me6)CrPh3]+3THF

Obedience to the 18e rule for [M(Ar)2] complexes: For [M(1l6-C6H 6)2] (M = Cr, Mo, W), the 18e
configuration is attained. They adopt the ferrocene type sandwich structure where 116-C6H 6 rings lie
ry
in the parallel planes. The bivalent metal ion, [M(1l6-Ar)2]2+ (M = Fe, Ru, Os) satisfies the18e rule; the
trivalent metal ion [M(1l6-Ar)2]3+ (1\1 = Co, Rh, Ir) also satisfies the 18e rule.
ra
It may be noted that sometimes to meet the requirement of 18e rule, 116-Ar may change into 114-Ar
or 112-Ar (described as haptotropic shift). The same situation for 'CsHs (i.e. lls-CsHs ~ 113-CsH s ~
ib
1l1_CsHs) has been already illustrated. One such example for C 6H 6 is:
yl
m
he
Au
lc
ea
# (bent mOiety
.
th
(18e) nonplanar)
(20e, unstable)
e/
[Fe II (lls-Cp)2] and [Mo(1l6-C 6H 6)2] (M = Cr, Mo, W) are isoelectronic (18e configuration). Here, in
ferrocene, Fe is in +2 oxidation state while in [M(1l6-C6H 6)2], the metal is in 0 oxidation state. Ferrocene
t.m
can be chemically or electrochemically oxidised to [FeIII(lls- Cp)2]+ but [Mo(1l6-C 6H 6)2] is more readily
oxidised to [M I(1l6_C 6 H 6)2]+. In fact, [Cr(C 6H 6)2] is readily oxidised to [Cr(C 6H 6 )2]+.
[Cr(C 6H6)2] + H+ ~[Cr(C6H6)J+ +~H2

e
er
It indicates that [M(1l6-C 6H 6)2] can lose an electron more readily. It is quite reasonable because Z*
H
for Fe(II) is greater than that of MO. This prediction is supported by the fact that [Mo(CO)3(1l6-C 6H 6)]
is having the more oxidative stability than [Mo(116-C6H 6)2] because the CO group is a better
1t-acceptor ligand than C6 H 6 . Thus, Z* in [Mo(CO)3(1l6-C 6H 6)] is more positive than that in
k
[Mo(1l6-C6H 6 )2]·
lic
In generq,/, the rf-arene complexes are more reactive and less stable than their corresponding
rf-Cp com~lexes. In fact, the dibenzene complexes, [M(11 6--e6H6)2](M=Cr,Mo, W) are air
C
sensitive.
Better 1t-acid ligands can easily replace the arene ligands.
[Cr (11 6--e 6H6)2] PF, ~ [ Cr (PF3)6 J;
[ Cr(CO)6] +[ Cr(11
6
--e6H6)2]~ 2[ Cr(CO)3 (11 6--e6H6)]
Reactivity of the coordinated arene: The entire 1t-electron cloud of the arene ring is involved in
coordination with the metal centre in the 116-arene mode. Thus, compared to the free arene, the
coordinated arene is relatively electron deficient. This is why, though the free arene is easily attacked
by an electrophile (i.e. electrophilic substitution), the coordinated arene is not so easily attacked by an
electropphile. Sometimes, the coordinated arene may respond to a nucleophilic attack. It supports
the electron deficient condition in the coordinated arene. The electron deficient condition of the coor-
dinated arene is supported by the following findings.
(i) Coordinated benzoic acid in [(1l6-C 6HsC02H)Cr(CO)3] is a stronger acid than free benzoic acid.
ry
(ii) Coordinated aniline in [(1l6-C 6H sNH 2)Cr(CO)3] is a weaker base than free aniline.
(iii) Nucleophilic attack can occur on the coordinated arene. This aspect has been illustrated in Sec.
ra
10.12.
(iv) [Cr(1l6-C 6H6)2] can be acetylated (i.e. Friedel-Crafts reaction, electrophilic substitution) but
ib
[(1l6-C6H6)Cr(CO)3] can be the acetytated with a difficulty. CO is a better n-acceptor ligand
yl
than C6H6. Thus, the metal centre is more electron deficient in [Cr(CO)3(1l6-C6H6)] then in
[Cr(1l6-C6H6)2]. It makes the coordinated C6H6 ring in [Cr(CO)3(1l6-C6H6)] more electron deficient.
m
It indicates the disfavoured condition for an electrophilic substitution on the coordinated arene.
(v) Unlike ferrocene, these arene complexes are labile.
he
[Cr(CO)6]+[ Cr(116-e6H6)J~2[Cr(CO)3 (11 -e 6H6)]
6
6
[ Cr(11 -e 6H6 )J + 6PF3~[Cr(PF3)6] + 2C6H6
lc
ea
Bonding in the arene complexes: It occurs so as in the metallocenes. In C6H6, there are six 1t-MOs
from which the LGOs can be constructed. These LGOs can interact with the metal orbitals to give the
th
molecular orbitals. The most important interaction involves the metal dxz and dyz orbitals (cf Fig.
e/
9.20.3.4).
Heterocyclic arene complexes: Thiophene, pyridine, pyrrole etc. containing the heteroatoms like,
t.m
S, N, P, etc. are also able to form the complexes. Some examples are given below.
~p AsD) «5;S-R
e
I I
er
Cr(CO)3
~AS R-S~
Cr
H
k
lic
Examples of some other sandwich complexes of chromium with 116-coordination are given below.
C
<r Cr
9.20.5 Cycloheptatrienyl Complexes: Cycloheptatriene and Tropylium Cation

In C 7H g (i.e. cycloheptatriene), conjugation is maintained over the six carbon atoms, but the hydride
abstraction from the )CH 2 group gives the C 7Hr cation which is planar and conjugation is maintained
over the seven 7-C atoms. C,H.j maintains the aromaticity. Both C 7H g and C7H.j can act as the 6e
H
ry
H
-H (cycloheptatrienyl or
ra
tropylium cation)
planar
ib
C 7 Ha (6e donor)
yl
(Cycloheptatriene)
m
nonplanar
donor ligands. For the C7H7-ligand, electron count depends on the consideration of the oxidation state
he
of the metal. It is illustrated below.
C 7H 7 as a radical, i.e. [Mo(117-C7H7)] (7e donor); C7H 7+ as a cation, i.e. [M-1(117-C7H7+)] (6e donor).
lc
When C 7H g acts as a 116-ligand, the 7th C-atom, i.e. CH 2 moiety is bent away from the coordination
sphere. However, the hydride abstraction from the CH 2 group gives 11 7-C 7H 7+. In fact, H- abstraction
ea
places the 7th C-atom in conjugation and the metal centre is formally oxidised. Thus, 11 6-
cyclohexatriene is converted into 11 7-cycloheptatrienyl (i.e. tropylium). It is illustrated below.
th
H
e/
H
t.m
"- --1- _.'

Mo(COb
e
[(1l6-C 7 Ha)Mo(CObl
er
Sometimes, C 7H g enters as a C 7H 7-moiety during complexation.

H
[ V(~5 -CP)(CO)4 ] + C7 H g ~[ v (T1 -CP)(T1 -C 7 H 7 )J + 4CO + ~H2

5 7
k
It may be noted that the nucleophilic attack on a tropylium complex (117.C7H7) gives back the
lic
cycloheptatriene complex (116.C7H's).

C
223~opm V
225 pm,'1 150 pm
@)
Fig. 9.20.5.1 Eclipsed sandwiched structure of [(117-C7H7)V(115-Cp)].
The sandwidh structure of [(fl'-C,H,)V(T1 5-Cp)] is quite interesting. The C 7H 7 and Cp rings are
eclipsed. The V - C(117-C 7H 7) distance 225 pm is very close to V - C(115-Cp) distance 223 pm. It is
possible for the closer distance of the 11 7-C7H7 ring.
The sandwich structures enjoy a kinetic stability (i. e. no site is kept vacant for the approach of the
attacking agent). The symmetrical sandwich involving only the 11 7-C 7H7 ring, i.e. [M(11 7-C 7H 7)2] is not
known but several sandwich complexes involving 117-C7H 7 and 115-Cp are known. [Cr(117-C7H 7)(115-Cp)]
ry
is prepared as follows:
ra
[(r{--C 6 H6 )Cr(Tl 5-Cp)] + C7Hs_Al_Cl_ 3
-...,{ (Tl 7 -C 7 H7 )Cr(Tl 5--.cp)r AICl;j
ib
1S20~-
yl
m
[(Tl 7 -C 7 H7 )Cr(Tl 5 -Cp)]
he
9.20.6 Coordinating Behaviour of Cyclooctatetraene (cot)
Cot may be synthesised as follows: lc

ea
Heating
th
•
e/
t.m
(dihalocyclobutene) Cyclooctatetraene
Cot possesses 8 x-electrons. Thus it lacks in aromaticity. Cot is well known to act as a 4e-donor
ligand (i.e. 114-mode) by using one butadiene like moiety. It can act as a 4e donor to each metal centre.
e
Sometimes, cot may function as a bridging ligand.

er
Because of the lack in aromaticity, CgHg is more flexible (compared to C 6H6 ) and.it may have two
conformations: tub and chair. In free state, CgHg predominantly exists in tub form but in complexes,
H
both the tub and chair forms are noted. Different modes of coordination of cot are shown in Fig.
9.20.6.1.
k
lic
C
M [(1, 3-11 4-cot)M(CO):J
c/ I"'c M = Fe, Ru
cot (chair cot (boat or tub form) #' C ~ (1l4-cot)
a III 0 (chair form)
o
cot as 1,3-11 4-diene
,-" Fe/C
__
4P
----
I t----++-~
\ ~O
ry
\o
ffi
ra
4
(tub form) 1, 5-,,4 or bis-,,4 (TJ -eot)
ib
Fluxionality (equivalence of protons) of
[(1 ,5-11 4-cot)Fe(CO)=J through a flipping
o m 0
o
yl
mechanism
cot as a bridging ligand,
bis (1,3-,,4-diene) (chair form)
m
he
lc
ea
th
(chai r form)
e/
Fluxionality (equivalence of protons) of

[(1 ,3-,,4-cot)Fe(CO)=J through a transanular [(1,2,5,6-,,4-cot)CO(,,5_Cp)]
cot as a 1,5-chelating diene
t.m
jump mechanism
(1, 5-,,4 or bis ,,2)
e
er
H
Cr(CO)3
k
cot as 1,3,5-,,6-triene cot as,,2

Bridging cot as bis-1 ,5-chelating diene
lic
bis (1, 5-,,4-diene)
~
-------- ...
---. r.--- ; ~
C
'..
L_
(tub form)
~ ,
.. ... _------' "
("a-CaH a)
,
Bridging cot as bis-1 ,5-chelating diene

Uranocene (Sigma + allylic)
bis (1, 5-,,4-diene) (Planar CaHa2-, 1De donor) 4e.donor
Fig. 9.20.6.1 Illustration of different modes of coordinating behaviour of cyc}ooctatetraene (cot).
It is evident from Fig. 9.20.6.1 that CsH s can bind the metal centre in different possible ways. The
energy difference for these different modes may not be very high. Because of this fact, the complexes
of CsHs are very often found fluxional.
CsHi-: CsH~- i. e. cot2- possesses lOn-electrons and maintains thearomaticity. Because of the
partial double bond character in each C-C bond, cot2- is not flexible and it is planar. In cot2-, the
10 n-electrons are placed in the lowest 5 n-MOs and 3 n-MOs are kept vacant. cot2- to act as a Tl S.cot2-
ry
as a lOe donor ligand, the metal centre should have the large (i.e. diffused) orbitals to interact
ra
effectively with the large ring. Moreover, the metal centre should have the sufficient number of
unfilled orbitals. In fact, the planar aromatic cot2- is not a promising ligand specially towards the
ib
transition metals because of two reasons: the metal d-orbitals are not sufficiently diffused to overlap
with the MOs of this large planar moieties; lack of proper symmetry reduces this overlapping efficiency.
yl
However, in some complexes, cot2- has been found to act as a 10e donor ligand. One such example is:
[(l1s-cot2-)Ti(115-CP-)]. Here, all the C-C bond lengths in cot are equal (-140 pm) and l1s-cot2- acts
m
as a 10e-donor ligand. [Ti(114-C sHs)(l1s-C sHs)] is also reported. In this regard, the structure of [Ti 2(CgHs)3]
he
is quite interesting. It is:
[(l1s-CgHs)Ti-J.!-(11 4, 11 4-CsHs)Ti(l1 s-CxH s)]
lc
There are two planar l1s-CsHsligands, and one puckered CsHg-ring bridges the Ti-atoms in a bis-11 4 -
ea
mode.
The proper symmetry match between the f-orbitals of f-block elements and the n-MOs of coe-
provides the better situation for complexation. This gives a more favourable situation for the early
th
members of 5f-series (i.e. actinides) for which thef-orbitals are more diffused. It may be mentioned
e/
that the 5f-orbitals are more diffused compared to the 4f-orbitals. The 5f-orbitals of the early members
of the series are more diffused compared to those of the late members of the series. Thus, the metals
t.m
like Th, Pa, U, Np and Pu appear to be the best candidates for complexation with cot2-. This
prediction has been supported by experimental findings. cot2- may be prepared from cot as follows:
Kin THF ) cot 2 - (C8H~- )_U_C_14~) [u (cod 2] i.e. [ U (1l 8 --cot)2 ]

e
(intense yellow) deep-green

er
(inTHF)
[U(Cot)2] may be also prepared in the direct reaction between the elemental uranium and cot (CgH s)
H
itself.
U + 2C gH g ~
k
[U(cot)2]
[U(cot)2] is [U(l1g-C sH s)2] (called uranocene). In this sandwich complex, the planar cot2-ligands are
lic
symmetrically positioned with respect to U(IV). In [U(cot)2]' all the C - C bond lengths (-139 pm) are
equal. The complex is paramagnetic (J.!eff = 2.43 BM) and looks green. It is pyrophoric (i.e. catches fire
C
in air) and it is not very much stable. Uranocene does not experience the electrophilic substitution.
It indicates that the n-electron cloud is somewhat pushed into the f-orbitals of U(IV).
Other related complexes are: [Th(l1s-C sHs)2] (colourless, called thorocene), [Pa(lls-C sH s)2] (yel-
low, called protoactonocene), [Np(l1s-C gH s)2] (yellow, neptunocene), [Pu(lls-C sH s)2] (red,
plutonocene).
Obviously, lanthanides (4f-series) are less promising for complexation with cot2- because the 4f
orbitals are relatively less exposed compared to the 5.forbitals. However, a few complexes like [Ln(COt)2]-
with Ln(III) have been reported.
EXERCISE 9

1. Define the term, organometallic compound. Discuss the important characteristic features of the
metal-carbon bond.
2. Illustrate the 18e rule in organometallics. How can you rationalise the 18e rule? Discuss the
ry
examples disobeying the 18e rule.
3. Discuss the bonding properties of the bridging and terminal CO groups.
ra
4. Discuss the factors favouring the bridged structure of carbonyls.
ib
5. Discuss the importance of n-back bonding in the stability of metal carbonyls.
6. Discuss the vco values to characterise the structure of carbonyls.
yl
7. Discuss the structural and bonding interactions in the polynuclear carbonyls.
8. Discuss the properties of carbonylates and carbonyl hydrides. Discuss the use of Collman's
m
reagent Na2[Fe(CO)4] in organic synthesis. Compare the uses of RLi, RMgX; Na[Co(CO)4] and
he
Na2[Fe(CO)4] in organic synthesis.
9. Discuss the different factors influencing the v co values.
10. Discuss the bonding interactions of terminal and bridging NO groups. Discuss the factors control-
ling the linear and bent M-N-O linkage.
lc
ea
11. Compare the bonding properties of (i) CO and NO+ and (ii) NO- and O 2 in terms of MOT.
12. Pure nitrosyl complexes are not generally stable but mixed nitrosyls are stable - explain.
13. Even pure nitrosyls are really the mixed ligand complexes-explain with examples.
th
14. Discuss the bonding and structure of Roussin's salts (both red and black salts), brown ring
e/
complex and nitroprusside.

15. What do you mean by nonclassical carbonyls? What is isocarbonyl?
t.m
16. Generally, vco falls when CO undergoes complexation, but there are cases where the reverse
situation arises. (Hints: Nonclassical carbonyls)
17. Discuss the common routes to synthesise (i) carbonyls, (ii) carbonylates, (iii) carbonyl-nitrosyls,
(iv) carboyl hydrides.
e
18. Discu~s the Bronsted acid properties of the carbonyl hydrides.

er
19. CN- is a n-acid ligand but it can stabilise both the low and high oxidation states of the metal centre
- explain with examples.
H
20. Discuss the bonding properties of isocyanide or isonitrile as a ligand. Compare with the
CO-complexes. Discuss the geometry of the M-CNR linkage and change in V CN value on
k
complexation.
lic
21. Discuss the different modes of binding of S02 as a ligand. Is it a n-acid ligand?
22. Discuss the different factors controlling the coordinating behaviour of phosphines and phosphites.
C
23. What do you mean by Tolman's cone angle? Discuss its significance. Failure of the 18e rule may
be sometimes interpreted in terms of the cone angle - illustrate.
24. Dinitrogen is not a potential ligand - explain in terms of its MO-diagram. Discuss the factors
controlling the stability of the dinitrogen complexes. Compare the ligating properties of the
isoelectronic species N 2, CO, NO+ and CN-.
25. Discuss the different modes of coordination by O 2 in terms of MOT.
26. During complexation, triplet O 2 may be converted into singlet O 2 - explain with suitable examples.
27. Discuss in detail the bonding interaction in the dioxygen adduct of Vaska's complex. Discuss the
position of v o- o and v c-o in the adduct.
28. Discuss the properties of dihydrogen as a n-acid ligand.

29. Illustrate the activation of O2, N2 and H2 through complexation.
30. Discuss the factors controlling the stability of M-C a-bond.
31. Give the examples and properties of the ionic organometallics.
32. Discuss the structures and properties of the alkyl, aryl and cyclopentadienyl complexes of the
alkali metals, alkaline earth metals and Zn-group metals.
ry
33. Hydrolysis of the 'M-R' bond goes through the push-pull mechanism.
34. Discuss the properties and structures of the organometallics of Gr. 13, 14 and 15 elements.
ra
35. Discuss the synthesis, bonding and properties of carbene and carbyne complexes.
36.. Discuss the bonding properties of alkenes, alkynes, dienes, allyls, cod, nbd, cot, cyclobutadiene,
ib
arenes, cycloheptatriene and cyclopentadienyls as the ligands.
yl
37. Discuss the bonding in Zeise's salt anion, butadiene complex, and allyl complex in terms of MOT.
38. Discuss the bonding mechanism in ferrocenes. Comment on its structure and reactivity. Comment
m
on the relative stabilities of the metallocenes.
39. Discuss the different modes of coordination of the Cp-ring, cod-ring, cot-ring, allyl anion, and
he
benzene.
40. Rationalise the apparently contradicting thermodynamic parameters
M-C bond distance (pm):

[Cr(CO)6]
192
lc [MO(CO)6]
206
[W(CO)6]
207
ea
M-CO bond energy (kJ mol-I) 107 (weakest) 151 178
VM-C (ratio): } . 2.03 1.81 (smallest) 2.15 (highest)
th
vc-o (ratio): (relatIve values) 17.87 18.12 17.70 (smallest)

Hints: (i) Many factors determine the bond energy (cf. corresponding Born-Habar cycle).
e/
(ii) VM-C value mainly depends on the efficiency of the M ~ CO n-back bonding and it follows
the order, W ~ CO ) Cr ~ CO ) Mo ~ CO. Consider the different factors like size of the
t.m
d-orbital, Z*-of the metal centre, steric factor, etc. to determine the said n-bonding.
41. Discuss the different types of sandwich complexes.
42. Discuss the reactivity of coordinated (i) alkene, (ii) alkyne, (iii) Cp, (iv) C6H6 , (v) allyl (vi)
e
cyclobutadiene.
er
B. Justify the following statements

H
1. Metal carbido and metal cyanido-complexes are not considered as the organometallic compounds.
2. Some authors exclude the metal carbonyls from the dictionary of organometallics.
3. Organometallics may be of both types - ionic and covalent.
k
4. Some compounds having the nonmetal-carbon bonds are also included in the broader area of
lic
orgametallic chemistry.
5. Organometallics may contain both the classical and nonclassical metal-carbon covalent bonds.
C
6. [(LiCH 3)]4, [Be(CH 3)2]n, [AI(CH 3)3]2 etc. are constituted by methyl bridging.
7. Simple metal-carbon a-bonded organometallics are well known for the main group metals but
rarely known for the transition metals.
8. In many organometallics, the delocalised n-electron clouds of the unsaturated organic compounds
are used for making the metal-carbon a-bonds.
9. Both the early and late members of a particular series of transition metals fail to form the stable
carbonyls.
10. Carbonyls of the heavier congeners of the transition metals are relatively less stable compared to
the those formed by the lighter congeners.
11. Pd, Ag, Au, Pt, etc. fail to form any stable carbonyl complex.
12. Ti and V form the relatively unstable carbonyls.
13. Positive oxidation state of the metal centres reduces the stability of their carbonyls.
14. The metals residing at the right bottom comer of d-block elements are the least suitable candi-
dates for the carbonyl formation.
15. The H 3BCO (borane carbonyl) is probably the unique example of the probable adducts formed by
ry
the main group elements with CO.
• In the adduct v eo stretching frequency is higher than that of free CO.
ra
16. In terms of the 18e rule, \\'e should expect [Ti(CO)7] but it does not exist.
17. [Ti(CO)6]2- (18e) is highly unstable and its isolation needs the large counter anions.
ib
• [Os4(CO)xl (x = 14, 15, 16), [(OC)5Cr(J.l-H)Cr(CO)5]- and [(OC)4Cr(J.l-H)2Cr(CO)4]2- obey
yl
the 18e rule.
18. Carbonyls prefer the low oxidation states of the metal centres but the highly reduced carbonylates
m
like [Cr(CO)4]3-, [Mn(CO)4]3-, [V(CO)5]3- etc. are quite unstable.
19. Mononuclear carbonyls should be handled very carefully.
he
20. [Ni(CO)4] is more toxic than either Ni or CO alone.
21. In terms of the 18e rule, [V(CO)6] should undergo dimerisation.
22. lc
Substitution of CO in metal carbonyls generally passes through the dissociative path rather than
the associative path.
ea
23. The 18e rule cannot distinguish the bridged and nonbridged carbonyls.
24. J.l2-CO and ketonic groups are similar in some aspects and dissimilar in other aspects.
th
25. Relative stability of the bridged and nonbridged tautomers of the carbonyls can be predicted in
terms of the metal-metal bond length and steric crowding around the metal centre.
e/
26. Lighter congeners prefer the bridged structure of the carbonyls while the heavier congeners prefer
the nonbridged structures.
t.m
27. Very often, in solution, the polynuclear the carbonyls may remain in an equilibrium mixture of the
bridged and nonbridged tautomers.
28. In [Fe3(CO)12] there are two bridging J.l2-CO groups while in [RU3(CO)12] or [OS3(CO)12] there is
e
no J.l2-CO group.
er
• Generally, the mononuclear carbonyls are colourless while the polynuclear carbonyls are
coloured.
H
29. Both the bridging J.l2-CO and J.l3-CO groups are considered as the 2e-donor ligands.
"'-
3D. For the J.l2-CO group along the M-M bond, the preferred M - C - M bond angle is 90°.
k
31. In [Fe2(CO)9] there are three J.l2-CO groups while in [Fe3(CO)12] there are only two J.l2-CO groups.
lic
32. In solution, [C0 2(CO)8] shows two v eo values while in solid state value it shows only one v eo
value.
C
33. [C0 2 (CO)s] can adopt the CO-bridged structure but [Mn2(CO)1O] cannot attain the bridged struc-
ture.
34. The number of bridging J.l2-CO group is different for [Fe2(CO)9] and [OS2(CO)9]'
35. In [C04(CO)12], there are two types ofvco values while in [Ir4(CO)12] there is only one type ofv eo .
36. In [Ir4(CO)12] there is only one type of v eo while in [C02Ir2(CO)12] there are two types of Yeo.
37. In CO, the lone pair resides on both the C and 0 ends, but CO coordinates through the C end.
38. If CO coordinates through the 0 end, then both the ligand ~ metal a-bonding and metal ~ ligand
n-bonding are weakened.
39. Generally, the J.l2-CO group binds symmetrically but sometimes it can bind unsymmetrically.
40. In [OS4(CO)14], there are four unsymmetrical J.l2-CO groups.

41. The unsymmetrical J.l2-CO groups (known as semibridging CO groups) are generally found in
the carbonyls of the heavier congeners.
42. [Rh6(CO)16] contains four J.l3-CO groups.
43. Depending on the conditions, the CO group can act as the 2e, 4e and 6e donor ligands.
44. Sometimes, the 1t-electron cloud of the C-O linkage can be utilised for metal coordination.
ry
45. The C-O bond order runs as: terminal-CO) J.l2-CO ) J.l3-CO.
46. Isocarbonyl metal complexes (having CO coordinated through the 0 end) can be only expected
ra
for the metals like Au, Ag, Pt, etc.
47. In the carbonyls of Ag+, Au+, Pt2+, etc., the v eo is higher than that of free CO.
ib
48. v eo runs as: terminal CO ) J.l2-CO ) J.l3-CO.
yl
49. [Ti(CO)6], [Pd(CO)4], [Ag 2(CO)6] are quite unstable.
50. Reductive carbonylation is an important route to synthesise the metal carbonyls.
m
51. Carbonylate anions as the nucleophiles can be used to synthesise the metal-metal and metal-
carbon bonds.
he
52. [Fe(CO)5] undergoes disproportionation in NaOH solution.
53. [C0 2(CO)s] undergoes disproportionation in presence of py or PPh 3.
lc
54. Reduction of metal carbonyls produces the carbonylate anions.
55. Depending on the conditions, carbonyl hydrides can act as the H+ donors.
ea
56. Sometimes, the carbonyl hydrides may act as the powerful reducing agents.
57. The Bronsted acidity of the carbonyl hydrides depend on many factors.
th
58. Very often, the metal carbonyl halides undergo dimerisation.

59. In [Ag(CO)]+ and [CIAu(CO)], the C-O bond is shorter than that in free CO but the reverse is
e/
true for [Ni(CO)4]'

60. The OC ~ metal a-donation and metal ~ CO 1t-donation have the opposing effects" (but of
t.m
different magnitudes) on the C-O bond length.

61. Both the terminal CO and bridging J.l2-CO groups can act as the 1t-acid ligands.
62. Both Zn 2+ and Ni(O) are isoelectronic but between these two, only Ni(O) can form the· stable
e
carbonyl.
er
63. The stability sequence runs as: [Ni(CO)4] ) [Pd(CO)4] ) [Pt(CO)4]; [Pd(CO)4]2+ ) [Pd(CO)4]'
64. (i) v eo in [M(CO)3(dien)], M = Mo or Cr ( veo [in M(CO)6]
H
(ii) veo for the trans-CO group in [Ph3PCr(CO)5] ( veo [Cr(CO)6]

(iii) Yeo: [Ni(CO)4] ) [CO(CO)4]- ) [Fe(CO)4]2-
k
(iv) Yeo: [Ti(CO)6]2- ( [V(CO)6]- ( [Cr(CO)6] ( [Mn(CO)6]+

lic
(v) Yeo: [Fe(CO)5] ~ [Ru(CO)5] ~ [OS(CO)5]; [Cr(CO)6] ~ [MO(CO)6] ~ [W(CO)6]

(more correctly, [MO(CO)6] ) [Cr(CO)6] ~ [W(CO)6])
C
[Hints: Consider the effects of effective nuclear charge; electronegativity, steric crowding, d-
orbital size on the M ~ CO 1t-bonding.]
(vi) 10Dq: [V(CO)6]- ( [Cr(CO)6] ( [Mn(CO)6]+
v M - e : [V(CO)6]- ) [Cr(CO)6] ) [Mn(CO)6]+; v eo : [V(CO)6]- ( [Cr(CO)6] ( [Mn(CO)6]+
(vii) Stability: [Ni(CO)4] ) [Pd(CO)4] ) [Pt(CO)4]
Yeo: [Ni(CO)4] ( [Pd(CO)4] ( [Pt(CO)4]
(viii) v eo : fac-[ MO(CO)3 (PF3)3J ) f ac -[Mo(CO)3 (PCI 3)3J
) f ac -[ MO(CO)3 (PCIPh 2 )3 J ) f ac -[Mo(CO)3 (PMe 3)3J

(ix) v eo : [Mo(CO)6] ) [MO(CO)3 (PPh 3)J) [Mo(CO)3 (NH 3)J
(X) [(T\S-cp) Mo(CO)J2 ~[(T\s-cp)MO(CO)21+2CO

v co =1915, 1960 cm- 1 v co =1859, 1890 cm- 1
65. Sometimes, veo of the terminal CO group lies in the normal range of veo of J.l2-CO groups.
ry
66. In [Mo(CO)3(dien)], [Fe(CO)4]2-, [Ti(CO)6]2-, v eo lies close to 1750 cm- 1 (a characteristic value
for the J.l2-CO group) though there is no question of the existence of J.l2-CO group in these
ra
mononuclear complexes.
67. In terms of the position of Yeo, [Pd(CO)4]2+, [Ag(CO)]+, [Hg(CO)2]2+, [Ir(CO)6]3+ , etc. are the
ib
examples of nonclassical carbonyls.
yl
68. Carbonyl clusters are generally formed by the heavier congeners in very low oxidation states.
69. [Fe2(CO)9] is diamagnetic but [V(CO)6] is paramgnetic.
m
70. Sometimes, the coordinated CO group can experience a nucleophilic attack.
he
• Such nucleophilic attacks occur when the 1t-bonding in the parent carbonyl is relatively less
efficient.
• Nucleophilic attack by OH- on the C-end of the coordinated CO group is the basic reaction for
lc
catalysis by the transition metals in water gas shift reaction (WGSR).
ea
• Fisher carbene syathesis is possible by using [M(CO)6] (M = Mo, W) but not possible if
started with [Cr(CO)6] or [Ni(CO)4]'
• [Cr(CO)5]2- is highly basic to extract proton even from the MeOH solvent.
th
• [Cr(CO)4]4- is strongly basic.

e/
• [(OC)sCr-H-Cr(CO)sr and [(OC)4Cr(Il-H)2crCCO)4J- obey the l8e rule.

t.m
71. The 1t-acceptor strength follows the sequence:

CN- (CO (NO+
72. Compared to CO, CN- is a better a-donor but a poorer 1t-acceptor.
e
• v CN =[Pt (CN)4 J2-) [Pd (CN)4 J2- ) [Ni (CN)4 J2- » CN- (free)
er
3 4 5
• V CN = [V(CN)6J -) [V(CN)6J -) [V(CN)6J - » CN- (free)
H
73. The following two complexes are trigonal bipyramidal.

• [Mn(CO)4(NO)] (NO as NO+ in the equatorial position)
k
• [Fe(CN)(CO)4]- (CN- in the axial position).

lic
74. The a-donor strength of the ligands runs as:

CN- ) RNC ) NO+ -- CO
C
75. S02 can act as a 1t-acid ligand.

76. S02 can act both as a Lewis acid and a Lewis base depending on the condition.
77. PF3 is a good 1t-acid ligand and the P - F antibonding orbitals is used for the 1t-acceptance.
78. Depending on the conditions, in the nitrosyl complexes, NO may remain as NO+, NO (neutral) or
NO-.
• Depending on the conditions, the M-N-O likage may be linear or bent.
• Depending on the conditions, in the M-N-O linkage, the lone pair may reside on N (i.e. bent
linkage) or on M (i.e. linear linkage) (cf M-CNR linkage).
• Depending on the conditions, NO can act as a 3e-donor ligand or as ale-donor ligand.
• During the coordination by NO, the metal centre may experience Ie-oxidation or Ie-reduction
depending on the conditions.
• For the early transition series members, coordination of NO as NO+ is encouraged while the
late members of the transition series prefer NO to coordinate as NO-.
• Presence of other n-acid ligands encourages the coordination by NO in the linear M-N-O
fashion.
ry
• Presence of other a-donor ligands encourages the coordination by NO in the bent M-N-O
fashion.
ra
• Coordinated NO is a polarisable ligand.
79. The VNO stretching frequency depends on the M-N-O angle in the nitrosyl complexes.
ib
80. NO can act ·as a bridging ligand.
yl
• The stretching frequency runs as:
vNO (J-!3-NO) ( vNO (J-!z-NO) ( J-!NO (terminal NO).
m
81. In [RuCI(NO)z(PPh 3)z]+' both the linear and bent M-N-O linkages are found.
he
82. In [lr(C 3Hs)(NO)(PPh3)z]+, both the linear and bent Ir-N-O may exist.
83. Co-N-O linkage is linear in [Co(diars)z(NO)]z+ but it is bent in trans-[Co(diars)z(NCS)(NO)]+.
84. Both [lr(CO)(CI)(NO)(PPh3)z]+ and [RuCI(NO)z(PPh3)z] are isoelectronic but the coordinating
behaviour of NO is different in the two cases.
lc
ea
Vaska complex [lr(CO)(CI)(PPh 3)z] experiences an oxidative addition with NO+.
85. In [Co(NH3)s(NO)]z+ and [Fe(NO)(OHz)s]z+ (i.e. brown ring complex), coordination by NO as
N0- is preferred.
th
86. In [Cr(CN)s(NO)]3- and [Fe(CN)s(NO)]Z-, NO coordinates as NO+.

e/
87. In the nitroprusside ion, nucleophilic attack on the coordinated NO occurs preferably.
88. Coordinating behaviour~ of NO in the nitroprusside and brown ring complex are different.
t.m
• In the brown ring complex, NO coordinates as NO- but the M-N-O linkage is almost linear.
89. Both the formulations, i.e. [FeI(NO+)(OHz)s]z+ and [FeIII(NO-)(OHz)s]z+ of the brown ring complex
can explain the magnetic properties and the observed M-N-O bond angle.
90. Pure carbonyls are well known but pure nitrosyls are rarely known.
e
91. [Fe(NO)4] is a mixed ligand complex.

er
• Pure nitrosyl complexes are generally the mixed ligand complexes.

92. Ligand substitution behaviours of the following isostructural and isoelectronic species are different.
H
[Ni(CO)4]' [Fe(NO)z(CO)z] and [Co(NO)(CO)3]

• Ni(CO)4 responds to the D-process while the said nitrosyl-carbonyl complexes respond to the
k
A-process.
lic
93. Roussin's salts are diamagnetic.

94. CO can stabilise only the low oxidation states of metals but CN- can stabilise both the low and
C
high oxidation states of metals.

• Stability order of the adduct, [lr(CO)zX(PPh3)z]: X = I > Cl.
• CN- favours the spin pairing because of its strong crystal field splitting power and good
nephelauxetic effect.
• CN- can act as an ambidentate ligand.
• CN- can act as a bridging ligand in different polymeric compounds.
95. The cyanido-complexes like [Ni(CN)4]2-, [Fe(CN)6]4- etc. can readily form the adducts with the
Lewis acids like BF3.
96. SOz can act as a n-acid ligand.
• S02 can bind with ~he electron rich metal centre as a Lewis acid.
• S02 can act as a hid:entate n-acid ligand.
97. The a-donor and n-acceptor strength of the ligands are:
a-donor: CN- ) RNC") CO
n-acceptor: CO ) RN~ ) CN-
• Isonitriles (i.e. isocyanides) stabilise both the higher and lower oxidation states of metals but
ry
CO can only stabilis,e the lower oxidation states.
• Aryl isocynides are the better n-acceptors than the alkyl isocyanides.
ra
• Position of the lone.pair on N or M determines the shape of M-CNR linkage (cf M-NO
ib
linkage).
~ ~
• M-CNR linkage may be linear (i.e. C - N -C ~ 180 0 ) or bent (i.e. C - N - C -140 0 ) de-
yl
pending on the conditions, (i.e. oxidation states of the metal and nature of R).
m
• The linear M-CNR linkage is preferred for the relatively higher oxidation states of the metal
centre and R = alkyl group.
he
• For the linear M-CNR linkage VCN is slightly greater than that of free RNC.
• For the bent M-CNR linkage, V CN is less than that of free RNC (generally, when R = Ar).
•
direction it is about 180 0 •
lc
In [Fe(CNBu t )5]' the C - N - C angle at the equatorial plane is about 140 0 while in the axial
ea
• Coordinated isocyanides may experience a nucleophilic attack to generate the Fisher type
carbene depending on the nature of metal centre.
th
98. In terms of Tolman cone angle, the ligands can be classified as the slim and fat ligands.
99. PF3 is a n-acid ligand but NF3 does not show this property.
e/
100. The n-acceptor strength of the P(III) ligands runs as: CO ~ PF3 ) PCl 3 ) P(OAr)3 ) P(OR)3 ) PAr3
t.m
) PR3
• PMe3 gives the 18e-product with Ni(O), Pd(O), Pt(O) but P(t-BU)3 gives the stable 14e product
with the given metals.
• [Ni(PF3)4] is well known but [Pt(PF3)4] is not known.
e
• Both [Ni(PMe3)4] and [Pt(PMe3)4] are known.

er
• Relative stability of the cis- and trans- isomers of [W(CO)4(PR 3)2] depends on the bulkiness
(measured by cone angle) of PR 3•
H
• From [MO(CO)6]' [MO(CO)3(PMe3)3] can be prepared but [MO(CO)3(PPr~)3] cannot be obtained.

101. Dioxygen is chemically inert as an oxidant towards the organic substrates but it can be activated
k
through complexation with the transition metals.

lic
• O 2 binds reversibly (X = CI) and irreversibly (X = I, CH 3) with [Ir(CO)X(PPh 3)2]'

• Dioxygen may coordinate as O 2 and O}- depending on the conditions.
C
• O 2 can bind as 111-02 and 112-02 depending on the conditions.

• O 2 can act as a bridging ligand.
• The C-O and 0-0 stretching frequency in the adduct formed by Vaska's complex,
[IrX(CO)(PPh 3)2] with O 2 depends on the nature of X (= CI, I, CH 3).
• The 0-0 stretching frequency in the adducts, hemoglobin-02 and hemerythrin-02 differs.
• [Co(salen)(B)] forms an adduct with O 2 where O 2 functions as a bridging ligand.
• Vaska's complex, [Ir(CO)CI(PPh 3)2] (say[IrL4]),
[IrL4] [IrL4(S02)] [IrL4(BF3)] [IrL4(1l2-02)] [IrL4(Dh] [IrL4(1l2-C 2F4)] [IrL4CI 2]
V eo (em-I): 1967 2020 2067 2015 2034 2052 2075
102. Dihydrogen can act as a n-acid ligand and it binds as 112-H2 just like C2~4 in Zeise's salt anion.
• [MO(CO)3(PPr~2] is a 16e compound, i.e. coordinatively unsaturated. Itcannot bind with the
ordinary ligand like CO, PR3 but can bind with H2 to give the dihydrogen complex.
• When dihydrogen binds as a ligand, sometimes it gives the dihydrogen complex (i.e. 112-H2)
H
and sometimes it forms the dihydrido complex (i.e. M ( ) through the 2e-oxidation of the
ry
H
metal centre (i.e. oxidative addition).
ra
H
• M( ~ M (11 2 - H 2 ).Strong n-donating metal centre favours the equilibrium towards the
ib
H
yl
left, i. e. dihydrido complex is preferred over the dihydrogen complex.
• [MoH 2(PR 3)5] is a dihydrido complex while [MO(CO)3H2(PR3)2] is a di,hydrogen complex.
m
(Hint: See Sec. 10.12.11).
• Sometimes, protonation of the metal hydride (i.e. M-H bond) bond gives the dihydrogen
he
complex.
• Oxidative addition of H 2 leads to activation of H 2.
103. Dinitrogen can act as a n-acid ligand like CO.

lc
• Activation of H 2 can be attained in presence of suitable metal complexes.
ea
• N2 and CO are isoelectronic but N2 is a much weaker ligand than CO.
• Carbonyl dinitrogen mixed ligand complexes are less stable than the corresponding carbonyl
th
complexes, e.g. [Cr(CO)5(N 2)] is less stable than [Cr(CO)6].

• [MO(CO)3(N 2)(PR3)2] is more stable than [MO(CO)5(N 2)].
e/
• In presence of the good a-donor ligands and relatively weaker n-acid ligands, the dinitrogen
complexes become more stable.
t.m
• Dinitrogen is chemically inert but it can be activated through complexation.

• Coordinated N2 is a better ligand than free N2.
• Coordinated N2 is more basic than free N 2.
e
104. N 2, NO+ and CO are the isoelectronic species. Among these, N2 is the least promising one as a
er
ligand.
• N 2 is a very poor a-donor ligand but it is relatively a better n-acceptor ligand.
H
• Stability of a M-N 2 bond mainly depends on the n-bonding.

• Both HOMO and LUMO of N2 are not suitable for N 2 to act as a ligand.
k
105. For the main group elements, M-C(lll) bond strength decreases for the heavier congeners while
the reverse is true for the transition metals.
lic
106. Carbanionic character in the M-C bond determines the reactivity of alkyl or aryl organometallics.
107. Hydrolytic cleavage of the M-R or M-Ar bond depends on two factors: ease of nucleophilic
C
attack and protolysis of the M-R or M-Ar bond. (Hints: Importance of the push-pull
mechanism)
108. To prepare a M-R bond through the transmetallation reaction, HgR 2 is commonly used.
109. Sodium naphthalide can be easily prepared and it can be used as a good reducing agent in organic
synthesis.
• Na+[ClOH s]- is an ionic compound but it is readily soluble in organic solvents.
• In Na+ L- salt, the ease of anion formation from the corresponding hydrocarbons follows the
sequence.
anthracene) phenanthrene) naphthalene) biphenyl) benzene.
• LiR is a typically covalent compound while CsR is a typically ionic compound.

• LiR is a good reagent for the synthesis of different compounds.
110. In solution, LiR (R = Me, Et, etc.) exists as a tetramer where R acts as a bridging ligand to give
the Li-CJl- Li electron deficient bonds.
111. In solid state, LiR (R = Me, Et) provides 7 and 10 coordination numbers to C and Li centres
respectively.
ry
• In solid state of LiR, agostic interaction may be quite important for its crystal structure.
• Polymeric structure of LiR may be broken in presence of suitable ligands like tmda.
ra
112. LiR or RMgX cannot tolerate moisture.
113. LiR finds many uses in organic synthesis.
ib
• LiR is a potential alternative to RMgX (Grignard reagent) in organic synthesis.
yl
114. On heating of LiEt, ethylene is released.
115. BeMe2 or MgMe2 is unstable in water.
m
116. BeMe2 and MgMe 2 remain as the polymers through the bridging action of Me-group.
• BeR 2 is a linear monomeric molecule through sp-hydridisation of the Be-centre but in its
he
polymeric form, it remains in sp3-hybridised state.
• The monomeric form of BeR 2 is preferred for the bulky R-group.
117.
lc
• The polymeric structure of BeMe2 is broken down in presence of the coordinating ligands.
The dimeric structure of alkyl beryllium hydrides is attained through the Be-H-Be bond not
ea
through the Be-R-Be bond.
118. Structure of RMgX·n(solvent) depends on the nature of solvent (say: ether, THF as solvents).
th
• In solution, RMgX remains in an equilibrium mixture of different compounds.

• Grignard reagent is widely used in organic synthesis.
e/
• Grignard reagent may also be used in the synthesis of organometallics.

119. Alkylmagnesium alkoxides (RMgOR') exist as dimers in solvents like THF but as polymers in the
t.m
weakly coordinating solvents.

• Depending on the condition, in RMgOR' structure, different types of bridges like Jl2-R,
· Jl2-0R, Jl3-0R may exist.
e
120. [Mg(C sH s)2] exists as a staggered sandwich having the D Sd symmetry.

• [Ca(C SHS)2] in solid sate, shows the bonding activity of the Cp-rings in different ways like 11 1-
er
Cp, 113-Cp and l1s-Cp.

H
• In the structure of [Be(Cp)2]' both 11 1- and l1s-Cp rings are present.

121. BR 3 is momomeric, AIR 3 is generally dimeric, GaR 3 and InR 3 are monomeric.
k
• In the dimeric structure of Al 2R 6 there are two types of M-C bonds.

• The AI-CIJl-AI bridge bond of Al 2Cl 6 is of different type compared to the AI-CJl-AI
lic
bridge bond of A12Me6'

C
"- "-
• AI-C~ -,AI < AI-CI~ -AI.

• The bridging efficiency runs as: R 2P- ) X- ) H- ) Ph- ) R-
• In A1 2R 4Ph 2 , the AI-Ph-AI bridge is preferred over the AI-R-AI bridge.
• BPh 3 and AIPh 3 are structurally different.
• BPh 3 is monomeric while AIPh 3 is dimeric.
• For the very bulky R-group, AIR 3 can remain as a monomer.
122. TIR 3 is triangular but TIRi is a linear cation.
123. The ease of hydrolysis follows the sequence:
AIR 3 ) GaR 3 ) InR 3 ) TIR 3
• BR3 is resistant to hydrolysis while AIR 3 hydrolyses very rapidly.

• Hydrolysis of the M-R bond requires the push-pull mechanistic path.
• An organic carboxylic acid can catalyse better than an inorganic acid in the hydrolysis of BR3.
• -OOH can catalyse better than -OH in the hydrolysis of BR3.
• Hydrolysis of BR 3 can produce boronic acid R 2BOH (i.e. incomplete hydrolysis) but hydroly-
sis of AIR3 produces AI(OH)3 (i.e. complete hydrolysis).
ry
• AIMe3 and GaMe3 undergo hydrolysis to different extents.
• Alcoholysis of GaMe3 gives Me2Ga(OR) while alcoholysis of AIMe3 gives AI(OR)3'
ra
• AIMe3 catches fire in H 20 or EtOH but not in ButOH.
• Alcoholysis of AIR 3 is a common route to synthesise Al-alkoxides.
ib
• AIR3 is a stronger Lewis acid than BR3 .
yl
• Lewis acidity runs as: AIR 3 ) GaR 3 ) InR 3 ) TIR 3 .
• BMe3 is a better Lewis acid than BPh3.
m
• The nature of the AI-CH 3-AI bridge is different from that of the AI-Ph-AI bridge.
124. Aluminum alkyls can act as a polymerisation catalyst.
he
125. TI(Cp) or In(Cp) possesses a pentagonal pyramidal geometry in gaseous phase but in solid state
they remain as the zig-zag chains.
126.
lc
• Compared to NaCp, TICp has got some advantages as a reagent in the synthesis reactions.
In the preparation of PbEt4 from EtCI, instead of pure lead, Pb-Na alloy is used.
ea
• PbEt4 is used as an antiknocking agen.t in gasoline.
127. Hydrolysis of the M-R bond is relatively more difficult for the Gr. 14 elements compared to
th
those of the Gr 13 elements.

• SiH 4 (silane) is more prone to hydrolysis than CH4 • (See Chapter 10, Vol. 2)
e/
• Hydrolysis of MR4 of the Gr. 14 elements is kinetically disfavoured.

• SiR4 is resistant to hydrolysis but R xSiX4- x is not so resistant to hydrolysis.
t.m
• In the Dydrolysis of R xSiX 4- x, the Si-X bond is hydrolysed instead of the Si-R bond.
• Hydrolysis of R xSiX4- x gives siloxanes while ammonolysis of R xSiX4- x gives silazenes.
128. Disilenes, R 2Si=SiR 2 are stable only for the bulky R-groups.
e
• Disilenes are the softer Lewis bases than the olet1ns.

er
• Disilenes are coloured while olefins are colourless.

• Disilene acts as a better Lewis base as well as a better Lewis acid compared to the olefins.
H
• Disilenes are the better n-acid ligands than the olefins.

129. Ph 3Si-H is a hydride donor while Ph 3Ge-H is a proton donor.
In R 2M=MR 2 (M = Ge or Sn), the double bond is weak and bent.
k
130.
• R 2M=MR 2 is planar for M = C and Si while it is nonplanar for M = Ge and Sn.
lic
131. [M(Cp)2] and [M(Cp)X] are angular (M = Ge, Sn).

• In solid state, [Pb(Cp)2] gives a polymeric structure in a zig-gag chain.
C
132. Organotin is industrially important because of its use as a stabiliser of PVC, as an agricultural
biocide and as an ant.ifouling agent.
133. MR 2 is linear (M = Zn, Cd, Hg)
• Lewis acid strength runs as: ZnR 2 ) CdR 2 ) HgR 2
• The ease of hydrolysis runs as: ZnR 2 ) CdR 2 ) HgR 2
• ZnR 2 can add to the )C = 0 group but CdR 2 or HgR 2 fails.
• [Zn(bipy)Me2] is more stable than [ZnMe2]'
• [CdR 2] can be used in the synthesis of ketones from acid chloride but the Grignard reagent
cannot be used for this purpose.
• CH3Hg+ is a long-lived species in environment.

• Hg(II)-C bond is not thermodynamically very much stable but it is kinetically resistant to
hydrolysis.
• RHgX may be ionic or covalent depending on the nature of X-.
134. Mercuration of the R-H bond can be easily done by using HgX 2.
• Organomercury(II) compounds generally show the coordination number 2 but in some cases,
ry
the coordination number may be increased to 3.
ra
• [(Cp)ZnCH 3] in solid state produces a zig-gag chain.
• In [Hg(CP)2]' 1l1_Cp ring is present but all the 5C- atoms appear identical.
ib
135. Alkyl or aryl compounds of the main group elements are relatively more stable compared to those
of the transition metals.
yl
136. Instability of the alkyl and aryl compounds of transition metals is due to the kinetic reasons not
m
due to the thermodynamic reasons.
137. Alkyl or aryl compounds of the transition metals can be stabilised if the other coordinated ligands
he
are the n-acid ligands.
• Sometimes, the alkyl or aryl compounds of the inert metal centres are fairly stable.
lc
• M-CH 2CH 3 bond is generally less stable than M-CH 3 bond.
• ' M-CH2CMe3 bond is generally more stable than M-CH 2CH 3 bond.
ea
• [Ti(bipy)Me4] is more stable than [TiMe4]'
• Though there is no possibility of {3-H transfer in TiMe4 and WMe6' they are unstable.
th
• M-Ph bond can experience neither a-H transfer nor ~H transfer, but many his-phenyl
compounds like cis-[Pt(PPh 3)2(Ph)2] are unstable.
e/
• Many alkyl hydrides are unstable due to alkane elimination.

• [M(bipy)Me2] (M = Zn, Cd) are more stable than [MMe2]'
t.m
• HeaviGr .congeners can stabilise the M-alky/aryl bond better than the lighter congeners.
138. v eo values significantly differ for [RMn(CO)s](R = CH3, CF3).
• veo appears at a higher frequency when [(Ph 3P - C SH4)Mo(CO)3] forms an adduct with BF3.
e
• v eo in [M(CO)s(L)] depends on the nature of n-bonding property of L.

er
• v eo values for the cis- and trans- CO groups in [M(CO)sL] are significantly different.
• More symmetric carbonyls show fewer number of absorption bands for CO stretching.
H
• cis- and trans- isomers of [M(CO)4L2] show different numbers of absorptions bands for CO-
stretching.
k
• All the bands due to CO-stretching in cis-[M(CO)4L2] are not equally strong.
lic
• veo bands are of different intensities in the isoelectronic species [V(CO)6]-' [Cr(CO)6] and
[Mn(CO)6]+'
C
139. IR-absorption spectra (due to CO stretching) of [(l1s-Cp)Fe(CO)2]2 are different in solid state and
gaseous phase. .
140. The bent linkages M - Nand M - 0 can be explained (approximately) by using the
same MO-diagram. "0 "0

• In the adduct M(02) formation, triplet dioxygen may be converted into the singlet O 2 depending
on the mode coordination by O 2.
• In the adduct M(02), O 2 may remain either as O 2- or 0 22- depending on the condition.
• CO as a ligand forms a linear linkage (M-C-O) while Oz as a ligand forms a bent linkage
M-O", .
o
• When Oz coordinates as l1z-0z, with the metal orbitals, 0, nand D-interaction can occur.
• The values of v o- o and v c- o in the adduct [IrX(CO)(l1z-0z)(PPh3)2] depends on X (= CI, I).
ry
• Oz can act as a bridging ligans.
• Both N z and CO are isoelectronic, but N z is a very poor ligand while CO is a promising 1t-acid
ra
ligand.
• In the adduct, M(N z), stability mainly depends on the efficiency of metal ~ N z 1t-back
ib
bonding.
yl
• Bonding interactions in l1z-0z and l1Z-CZH4 ligands are of different types.
141. In the Zeise's salt anion, [Pt(l1z-CzH4)CI3]-, C-C is perpendicular to the plane of 'PtCI 3' moiety.
m
• Coordinating behaviours of C ZH 4 and C Z(CN)4 are different.
• In some cases, the C-C bond length of the coordinated C Z(CN)4 is close to the C-C single
he
bond.
• Rotation of the coordinated l1Z-CZH4 around the metal-C zH 4 Jl-bond depends on many factors.
lc
• In [Pt{ C Z(CN)4}(PR 3)z], the C-C bond length is close to the single bond.
ea
142. In [M(CO)6]' all the CO-groups can be substituted by PF3 but not by PR 3.
143. AgCI0 4 is not soluble in water but soluble in benzene.
144. Butadiene, cod, nbd, cot, cyclopentadiene can act as the chelating ligands.
th
145. In the metal-butadiene complex, depending on the conditions all M-C linkages may be equiva-
e/
lent or nonequivalent.
• Coordinating behaviour of 114-butadiene can be understood from the MO-picture of butadiene.
t.m
• Sometimes, butadiene coordinate as a l1z-ligand.

• Coordinating behaviour of C 4H 6 in [(C4H6 )Fe(CO)3] and [(C 4 H f JFe(CO)4] is different.
• Nucleophilic attack on a free olefin is disfavoured but it can happen on a coordinated olefin.
• Like the olefins, the silenes (RzSi===SiR z) can act also as the n-acid ligands.
e
• C Z(CN)4 on coordination may produce a metallacyclopropane fragment.

er
146. An alkyne (RC-CR) can act as a 2e-donor ligand like the olefins but sometimes, it can act as
a 4e donor ligand.
H
• Coordinated alkyne may produce the metallacyclopropene or metallacyclopropane depending

on the condition.
k
• In the metal-alkyne complex, 0-,11:- and &- bonding interactions may occur. --
lic
• Alkynes may also act as the bridging ligands.

• Coordinated alkyne may experience a nucleophilic attack.
C
147. Coordinating behaviour of the allyl ligand can be explained in terms of its MO-diagram.
• Allyl group (C 3Hs-) may function either as a 2e-donor ligand or as a 4e-donor ligand depend-
ing on the condition.
• Stereoisomerism may arise in the allyl complexes.
• Allyl complexes very often show the fluxionality.
• Sometimes, Cp, azulene and indenyl groups may also coordinate through the 113-allyl moiety.
• Protonation of the dien-complexes may lead to allyl complexes.
• Sometimes, 114-butadiene and 113-methyl allyl complexes are interconvertible.
148. [Fe(C sH 7 )z] is called an open ferrocene.
•11 I-ally may change to 113-all y with the expulsion of a 2e-donor ligand.
•CsHg (1, 3-pentadiene) can bind like a butadiene through the 114-coordination but it can bind
as a l1S-ligand on oxidation.
• Proton abstraction from the monoolefinic complex may lead to the allyl complex.
149. Many carbocycles can act as the 1t-acid ligands.
• cot2- is not a promising ligand.
ry
• cot2- as a ligand prefers the metals in the sequence:
actinides) lanthanides) transition metals.
ra
• CgH g can coordinate in different ways (11 2, 11 4, 11 6 , etc.)
• CgHg can act as a chelating diene and also as a bridging ligand.
ib
• CgH g can exist in both chair and tub forms.
yl
• Complexes formed by CgHg are very often fluxional.
• [U(~g-CgHg)2] is a sandwich type complex.
m
• Early members of the 5f-series are the best candidates to use CgHg2- as a ligand.
150. 114-C4H4 can act as both the 4e and 6e donor ligands depending on the condition.
he
• Free cyclobutadiene (C 4H 4) is unstable but it can be trapped when it remains coordinated.
• Electrophilic substitution on the coordinated C4H42- can occur.
151. Cp-ring can coordinate in different possible ways. lc
• Bonding in ferrocene can be understood in terms of the 1t-MOs of the Cp-ring.
ea
• In the metallocenes, 18e rule is not strictly maintained.
• Sometimes, it may be difficult to predict the magnetic properties of the metallocenes from the
th
general MO energy diagram of metallocenes.

• [Mn(l1S-C sH s)2] is high-spin while [Mn(l1s-CsMe)s] is' low spin.
e/
• [Mn(l1S-~p)2] is high spin while [Re(l1s-Cp)2] is low spin and [(l1s-Cp)2ReH] (bent metallocene)
is diamagnetic.
t.m
• [Cr(Cp)2] shows an anomalous magnetic moment.

• Metallocenes deficient of 18e configuration very often adopt the bent structure through the
addition of extra ligands.
e
152. Metallocenes' of the early members of the.! st transition series are high spin while the metallocenes
er
of late members of the series are low spin.

• [Fe(Cp)2] is both kinetically and thermodynamically stable.
H
• [M(*Cp)2] is kinetically more stable than M(CP)2'

• Both [Fe(Cp)2] and [CO(CP)2]+ are isoelectronic (18e) but [CO(CP)2]+ shows the more oxidative
k
stability.
• Magnetic properties of [Mn(J1 5-C sHs)2], [Mn(l1s-C sH4Me)2] and [Mn(l1s-C sMes)2] are different.
lic
• [Co(Cp)2] and' [Ni(Cp)2] a~v -sensitive to oxidation.

C
• [V(CP)2]' [Cr(Cp)2] tend to add ligand(s).

• Azulene and indenyl group can provide the Cp-ring for coordination.
• The staggered configuration of [Fe(Cp)2] in solid state is due to the crystal packing factor.
• In ferrocene, rotational energy barrier between the staggered and eclipsed configurations is not
very high.
• Cyclopentadienyl complexes are very often fluxional.
• Metallocenes having the electron count less than 18, very often attain the bent metallocene
structure through the addition of extra ligand(s).
• With the successive addition of 2e donor ligands, coordinated l1s-Cp experiences the
transformation,
(11 5-Cp ~ 11 3-Cp ~ 11 1-Cp) (haptotropic shift )-.

(Slipped ring system)
153. [Mg(CP)2] hydrolyses readily but [Fe(Cp)2] does not.

154. [Cr(C 6H 6)2] is a sandwich compound.
• Coordinated 116-C 6H 6 can experience a nucleophilic attack while the free arenes generally
ry
experience an electrophilic substitution.
• Acetylation on [Cr(CO)3(116-C 6H 6)] is more difficult than on [Cr(116-C 6H 6)2].
ra
• Coordinated aniline in [(116-C 6H sNH 2)Cr(CO)3] is a weaker base than free aniline.
155. 116-C6H 6 can experience the haptotropic shift, i.e. 116-C 6H 6 ~ 114-C 6H 6 ~ 112-C 6H 6.
ib
• 116-C6H 6 is planar but 114-C6H 6 is nonplanar.
yl
• [Fe(l1S-C sH s)2] and [Cr(116-C 6H 6)2] are isoelectronic (18e) but [Fe(l1S-C sH s)2] registers more
oxidative stability. In fact, [Cr(116-C 6H 6)2] is readily oxidised to [Cr(116-C 6H 6)2]+.
m
• Compared to [M(116-C 6H 6)2], [M(CO)3(116-C 6H 6)] shows the more oxidative stability (M = Cr,
Mo, W).
he
156. C 7H g (cycloheptatriene) can coordinate as 116-C 7H g but hydride abstraction from C 7H g gives the
11 7-C 7H 7+ coordination. (Both 116-C 7H g and 11 7-C 7Hr act as the 6e-donor ligands).
• C 7H g can coordinate in different ways. lc
• 116-C 7H g is nonplanar while 11 7-C 7Hr is planar.
ea
• Nucleophilic attack by H- on the tropylium complex gives the cycloheptatriene complex.
157. Structural formula representation of the carbonyl hydrides having the strong Bronsted acidic
th
property (e.g. [HCO(CO)4]) is a matter of debate.

• Carbonylates acting as the nucleophiles can be used to produce the M-C and M-M bonds.
e/
• Relative nucleophilicities of carbonylates: [Re(CO)s]-) [Mn(CO)s]-) [CO(CO)4]-; [W(CO)3(CP)]-

) [MO(CO)3(CP)]-) [Cr(CO)3(CP)]-. Hints: Compare the acid strengths of the conjugate acids.
t.m
• Ph(Et)HC*CI + [Mn(CO)s]- ~ inversion of configuration at C. .

158. The carbonyl halides like [Rh(CO)2CI]2' [Ir(CO)CI(PPh 3)2] do not follow the 18e rule.
• The highly electronegative metals like Au, Pt, etc. cannot form the stable binary carbonyls but
e
they can form the fairly stable carbonyl halides.

er
• [Ni(CO)4] is stable while [Ni(CO)3X]-, [Ni(CO)2X2]2- are unstable. On the other hand, [Pt(CO)4]
is unstable but [Pt(CO)3X]+, [Pt(CO)2X2] are fairly stable; X- = halide.
H
• For [Ni(CO)2X2]2-, the stability order runs as: 1- ) Br-) CI- but for [Pt(CO)2X2], the stability
order runs as: CI- ) Br-) 1-.
k
• [Pt(CO)4] is unstable but [Pt(CO)2(PPh 3)2] is stable.

lic
• [Co(CO)4I] is unstable but [Co(CO)3I(PPh3)] is stable.

Hints: (i) For [Ni(CO)3X]- and [Ni(CO)2X2]2-, with the increase of electronegativity of X, the
M ~ n*(CO) (n-back bonding) is hampered, (ii) For [Pt(CO)2X2] and [Pt(CO)3X]+, the M ~
C
CO a-donation is favoured for the more electronegative X. (iii) PPh 3 is a good a-donor ligand
but it is a poor n-acceptor (cf. Fig. 9.4.11.3, competitive n-bonding).
• Bridged binuclear carbonyl halides are cleaved in presence of the nucleophiles.
159. In [Co(CO)(NO)(PCl xPh 3_x )2] (x = 0, 1,2, 3), the values of VNO and v eo increase with the increase
of the value of x.
Organometallic Reactions and the
ry
Reaction Pathways: Reactivity of
ra
Coordinated Ligands: Catalysis
ib
yl
m
10.1 IMPORTANTTYPES OF REACTIONS OF ORGANOMETALLIC COMPOUNDS
(i) Acid-base.adduct formation:
he
lc
ea
(Coordinatively
unsaturated) (18e)
th
(ii) Ligand substitution reaction:

e/
[Ni(CO)4] + PPh 3 ~ [Ni(CO)3(PPh 3)] + CO

t.m
[Cr(CO)o] + PMe3 ~ [Cr(CO)S(PMe3)] + CO
[Cr(CO)6] + PMe 3 ~[Cr(CO)5PMe3] + CO
=H, R):
e
(iii) Migratory insertion into the M-X bond (X

er
CO insertion, olefin insertion.

"
(iv) Oxidation: [Mn2(CO)1O] + Br2 ~ 2[MnBI:(CO)s].
H
(v) Oxidative addition:

k
/H R
lic
LIlM+H2~LllM\. ~ LnM R-X lLnM(

H X
C
(vi) Reductive p-elimination: The reverse reaction of oxidative addition.

(vii) Reactivity of coordinated ligands: This aspect has been discussed in detail later on.
(viii) Scrambling (i.e. redistribution of ligands): These are discussed later.
1502
ORGANOMETALLIC REACTIONS AND THE REACTION PATHWAYS: REACTIVITY OF COORDINATED LIGANDS: CATALYSIS 1503
(ix) Metal carbo~yisas nucleophiles (cf. Sec. 10.4):

[Mn(CO)s]- + CH 3- I ~ [M(CH 3)(CO)s] + 1-
[CO(CO)4r + RCO-I ~ [(OC)4CO-~-R] + 1-
ry
[Mn(CO)~-+ ReBr(CO)s ~ [(OC)sMn-Re(CO)s] + Br-.
(x) Carbonylate anions as the conjugate Bronsted bases (cf. Secs. 9.4.7E, 9.4.17, 10.4): This is
ra
evident from the pKa values of the corresponding conjugate acids. The pKa values in CH3CN solvent
are given below:
ib
[HCO(CO)4] (8.3); [H 2Fe(CO)4] (11.9,21.5); [HMo(CO)s]; (15.1); [HRe(CO)s] (21.1)
yl
The corresponding pKa values in water are obtained as follows:
m
pKa(H 20) = pKa(CH 3CN) - 7.5
Thus pK a values of [H 2Fe(CO)4] in aqueous media become
he
pKal = 11.9 - 7.5 = 4.4; pKa2 = 21.5 - 7.5 = 14.0
The acid strength largely depends on the stabilisation of the conjugate base. The conjugate bases
lc
like [CO(CO)4r, [V(CO)~-, etc. are stabilised due to delocalisation of the negative charge through the
ea
metal ~ ligand n-back bonding in presence of the strong pi-acid ligands like CO. In fact, replacement
of CO by a weaker 7t-acid ligand like PPh3 will weaken the acid strength (cf. Secs. 9.4.7E, 9.4.17).
[HV(CO)6]' [HCO(CO)4] (pK a ~ 1.0) ) [HCo(CO)3(PPh 3)] (pKa ~ 7.0); [HV(CO)6] » [HV(CO)3(PPh 3)3]
th
Here it may be pointed out that in the conjugate acid, i. e. protonated species, generallly the M - H
e/
bonds are present (cf. PMR spectra, Secs. 12.2.6, 12.2.19).

(xi) Substitution vs. cluster fragmentation: Fragmentation leads to the rupture of M-M bonds to
t.m
produce the mononuclear carbonyls from the polynuclear carbonyls, (see Sec. 10.2.6).
These different types of reactions will be discussed in the next sections in detail.
IUPAC-2005 recommendation: Formula representation

e
In terms of the IUPAC-2005 recommendation (cf. Sec. 1.15.2), the carbonyl hydrides should be
er
represented (placement of the ligands in an alphabetical order) as: [CO(CO)4H], [Fe(CO)4(H)2],

etc. But this practice has not been followed here. In terms of the longstanding convention, these
H
are written as [HCO(CO)4], [H 2Fe(CO)4], etc. Moreover, for the better understanding of the
organometallic reactions, the IUPAC-2005 recommendation has not been strictly always followed
k
to represent the structural formulae of the organometallic compounds in this chapter.

lic
10.2 LIGAND SUBSTITUTION REACTIONS OFTHE CARBONYL COMPLEXES

C
10.2.1 Effect of Electronic Structure on the CO Substitution Process

(i) 18e-rule: If the starting complex already maintains the 18e-count then it favours the dissociative
path to generate the activated complex/intermediate of lower coordination number to possess the 16e-
count. In such cases, if the associative pathway is invoked to operate, then it will lead to the formation
of an energeticall~ unfavourable 20e-activated complex/intermediate.
On the other hand, the 16e-organometallic compounds will favour the associative path leading to
the formation of an 18e-activated complex/intermediate. In such cases, the dissociative path will lead
to the formation of a 14e-activated complex/intermediate which is energetically unfavourable.
(ii) Apparent violation of the 18e-rule (cf Sec. 9.6.6): When the organometallic compound contains
116-C6H6 or 115-Cp or 113-allyl or NO, with the approach of the entering nucleophile the I8e-compound
may rearrange as follows:
• T1 5-Cp (5e-donor) ~ T1 3-Cp (3e-door),
If Cp is considered to exist as Cp- (i.e. 61t electron system), then 115-Cp- (6e-donor) changes to
113-Cp- (4e donor). Obviously, 113-Cp- is isoelectronic with 113-allyl. It may be noted that 113-allyl
ry
(4e-donor) may change into 111-allyl (2e-donor) through slippage. In the same way, 113-allyl may be
ra
considered as a 3e donor and 11 I-allyl may be considered as Ie-donor.
H 2C
ib
M
@ 0
'CH
I l CH
yl
2
HC H 2C M
~CH 2
m
M M
(lls-Cp-) (1l3-CP-) ) (1l1-C3Hs ) (1l3-C3Hs )
he
)
V V
lc
• Change of NO+ mode of coordination to NO- mode of coordination (cf Sec. 9.6) is illustrated
below.
ea
M=N=O (NO as 3e-donor)~M - N (NO as Ie-donor).
~
th
o
e/
The change in the mode of coordination for the said ligands arises to generate the electron definient
metal centre (e.g. I8e-count ~ I6e-count) which can accommodate the entering nucleophile to initiate
t.m
the associative path. Thus this type of organometallic compounds of I8e-count can particpate in the
associative reactions (cf Sec. 9.6.6 for details). Here actually the lower electron count centers are
generated during the approach of the nucleophile (cf electromeric effect in organic chemistry).
(iii) Nature of the spectator ligands: Strength of the M-CO bond largely depends on the
e
metal ~ CO 1t-back bonding. If the spectator ligand is a strongly basic ligand, then the increased
er
electron density on the metal centre will favour the metal ~ CO back bonding to strengthen the
M-CO linkage. It will disfavour the substitution of CO.
H
The donor properties of phosphine derivatives vary in the sequence:

PF3 « P(OAr)3 ( P(OR)3 ( P(Ar)3 ( P(R)3
k
(R = alkyl group, Ar = aryl group).

lic
If the 'CO' groups are gradually replaced by the PR 3 groups then after the entry of two or three PR3
groups, further reaction may fail to go on.
C
In [M(CO)5L] (C 4v symmetry, L = is a 1t-donor ligand, e.g. Br-), the equatorial four M-CO bonds
(i.e. bonds cis to L) are relatively weaker than the trans-axial M-CO bond (i.e. trans-bond to
the M-L bond). This can be explained by orbital overlap model (Figs. 9.4.11.5, 10.2.1.1). Two metal
d-orbitals are available for 1t-interaction between L and its trans-carbonyl group.
In fact, this 1t-interaction between L and its trans-CO ligand via two metal d-orbitals will strengthen
the M-C bond (trans- to L) if L is a 1t-donor ligand. This 1t-donor property of L, will facilitate the
metal ~ CO 1t-back bonding to strengthen the 'M-C' linkage. For the 4 cis-CO groups, the picture is
different. One d-orbital of the metal centre can mediate this type of 1t-interaction between L and two
cis-CO groups (which are mutually at the trans- positions). Thus, the 2. cis-CO groups interact with the
n-donor L through one metal d-orbital while the trans-CO (with respect to L) group can utilise two
metal d-orbitals to interact with the n-donor ligand L. Consequently, the metal ~ CO 1t-back bonding
is more pronounced for the trans-CO (with respect to L) compared to that in the 4 cis-CO groups. The
1t-bonding interaction suggests that if L is a 1t-donor ligand,
'M-C' bond strength (jor trans-CO) ) M-C bond strength (cis-CO groups).
If L is a 1t-acceptor ligand, the reverse trend will prevail, Le. 'M-C' bond strength (for trans-
ry
CO) < 'M-C' bond strength (cis-CO group).
ra
Explain:
ib
[ M(CO)6]
PR 3 (excess)
>[ M(CO)6-x (PR 3 tJ, X = 1,2,3
yl
( M(CO)6]
PF3 (excess)
>[ M(CO)6-x (PF3 tJ, = 1,2, ,6
m
X
tJ,
he
PF3 (excess)
[Ni(CO)4] >[Ni(CO)4-x (PF3 X = 1,2, ,4
Hints: Pi-acceptor strength, PF3 ) CO ) PR3 • Gradual substitution of CO by PR3 strengthens the
lc
residual M-CO bonds while gradual substitution by PF3 weakens the residual M-CO bonds.
ea
Explain the order of Veo:
J:
th
[ M (CO)s (PR 3 ) v CO(trans) < v CO(cis), < vco of [M(CO)6 ];( cf. Fig. 9.4.11.5)
e/
cis, trans with respect to PR 3

t.m
y
e
L
er
I/CO
;------. X
OC-M-CO
H
oc/I z
C
k
·0
lic
[ML(CO)5l
(C 4V )
C
d xy (L) - d xy (M) - 1t~ (CO )CiS

d xy (L) - d xy (M) - 1t: (CO)trans
d yz (L) - d yz (M) - 1t~ (CO)trans (not shown in this figure)
Fig. 10.2.1.1 Pi-bonding interaction between L(n-donor) and cis-CO and trans-CO via the metal d-orbitals in [M(CO)sL]
(ef Fig. 9.4.11.5). .
The 1t-bonding interaction is shown in Fig. 10.2.1.1. The prediction is supported by the fact:
In [MnBr(CO)s] (C 4v symmetry) where Br- acts as a 7t-donor ligand, the four cis-equatorial
Mn-CO bonds are weaker than the trans-axial Mn-CO bond. In such cases, the equatorial carbo-
nyl groups are substituted faster than the axial carbonyl group. The CO exchange rate for [Mn(CO)sX]
runs as: X = CI ) Br ) I. 1- being the most polarizable and least electronegative one pushes the
maximum electron cloud to strengthen the Mn-CO bond, i.e. Mn-CO bond is the strongest one for
X = I and it reacts slowest. All these support the dissociative activation.
ry
The M-CO bond strength effect (influenced by the spectator ligand) actually represents the ground
state effect that may not have always a strong command on the activation energy that controls the
ra
reaction rate process. To have the magnitude of activation energy both the ground state effect and
transition state effect are to be considered simultaneously as the energy difference between the ground
ib
state and transition state gives the measure of activation energy. Thus stabilisation of the transition
yl
state is of an important consideration to predict the favour in the rate process. This is illustrated in
the following examples.
m
[MnBr(CO)s] and [Mn(CO)~+
he
In [MnBr(CO)s], the n-donor property of Br- stengthens both the cis- and trans-CO bonds (where
the trans-bond is strengthened more). In [Mn(CO)6]+' absence of any such n-donor ligand cannot
strengthen the M-CO bond in this way. Thus in terms of the ground state effect, [MnBr(CO)s] should
lc
react slower than [Mn(CO)6]+ in the CO substitution process. But astonishingly, [MnBr(CO)s] is more
ea
reactive than [Mn(CO)6]+. Another observation is that [M(CO)sL] (L = 7t-donor ligand) experiences a
stereospecific substitution to give a cis-product, i. e.
th
[M(CO)sL] :~~ )cis-[M(CO)4(L)(L')]

e/
All these observations can be rationalised in terms of the transition state effect. It has been already
mentioned that in [M(CO)sL], the cis-CO groups are relatively weakly bound. In the dissociative
t.m
path, one cis-CO is lost to give the 5-coordinate square pyramid which rearranges immediately to the
trigonal bipyramid (tbp) which is stabilised better due to the n-bonding effect. In the trigonal bipyramid
geometry, the nonleaving n-donor ligand L occupies one equatorial position. This tbp geometry is
stabilised by the 1&-donor property of L. This n-donor property of L strengthens the n-acceptance of the
e
CO groups residing in the equatorial plane. Entry of L' to this trigonal bipyramid geometry gives the
er
cis-product. L' enters along the edges (of the trigonal basal plane) in the region where the electron
depletion is maximum due to the two electron withdrawing CO groups residing in the basal plane. It
H
explains the origin of the cis-product. Here it may be mentioned that the n-donor property of L can also
stabilize the 5-coordinate square pyramidal species (cf Fig. 5.21.1) that can also give the cis-product.
k
lic
L
L',,- :'1 '-- ..J L'
I I
C
M~,
OC"" /CO
OC /
M
I"" CO
CO
--eo
--~..
~
(rds)
OC"" /CO
M
I "" CO
CO
fast
(square pyramid) " " "

OC ,;
.. OC-------:.CO
(tbp)
CO +L'
(fast)
+L'
I
.. cis-[M(CO)4(L)(L')]
If the tbp geometry is sufficiently long-lived to experience the rearrangement, then a mixture
of cis- and trans- product will be obtained. The steric requirement may favour the trans- product.
In terms of stabilisation of the trigonal bipyramidal activated complex/intermediate by the n-donor

nonleaving group, the higher reactivity of [CrBr(CO)s]- than that of [Cr(CO)6] is understandable.
The same argument can explain the higher reactivity of [Cr(CO)s(PPh3)] (where PPh 3 is a good
a-donor but a poor n-acid ligand; cf Fig. 9.4.11.5) than that of [Cr(CO)6].
(iv) Steric effects: Stenc crowding favours the dissociative path and disfavours the associative
path.
ry
e
Reactant
ra
(
,[M(CO)6] -------- [M(CO)6]---"
(18e) (1ge) (dissociative path)
ib
co
yl
m
[M(CO)sL] ~----';~-[M(CO)sL]~ [M(CO)sl-
(18e) (1ge) \ (He)
he
L
lc
Scheme 10.2.1.1 ETC (electron transfer chain) reaction through the formation of anion radical.
ea
(v) Electron transfer initiation: Electron transfer can produce a cation radical (i.e. oxidation) or an
anion radical (i.e. reduction) that may participate in chain reactions (as in free-radicals) to give the
th
substituted product. Such reactions are described as the electron transfer chain (ETC) reactions.
In the ETC reaction involving the formation of an anion radical (Scheme 10.2.1.1), the 1ge-species
e/
experiences a dissociative activation in a reasonable way for the substitution process. To initiate the
process, i. e~ Je reduction of the starting complex, chemical method, electrochemical method or photo-
t.m
chemical method may be used. Here it may be mentioned that when the reaction will continue, the
reactant should be capable to oxidise the 1ge-species [M(CO)sL]- i.e. [M(CO)6] should a better electron
acceptor than the product [M(CO)sL]. This condition is maintained if L is a poorer 1t-acceptor than
CO. Thus for L = PPh 3 , the reaction can go on.
e
Similar ETC reaction through the formation of cation radical like [M(CO)sL]+ (17e-count) can also
er
be realised.
H
10.2.2 General Rate Law for the Nucleophilic Substitution of Metal Carbonyls
k
For the following typical substitution reaction.

lic
[LM(CO)n] + L' ~ [LL'M(CO)n_tl + CO, (L may be CO also)

The rate law is:
C
rate = (k) + k2 [L'])[LM(CO)n]

This two term rate law, indicates two parallel reactions: one first-order path (i.e. k)-path) and
another second-order path (i.e. k2-path). It reminds the two term rate law found for the substitution
reactions of square planar complexes where both the pathways are the associative pathways. But in the
present case, the first-order term arises from the dissociative path (D-path) and the second order
term probably arises from the interchange (I) path which may vary from Id to la depending on the
conditions. Thus the origins of the two term rate law for the square planar complexes and metal
carbonyls are totally different. It again reflects the limitation of the rate law to identify the reaction
mechanism.
• k 1-path (dissociative D path):

k, k
M-CO~M+CO, M+L~M-L
k_ 1
k1k[M-CO][L]
Rate = [ ] [] ,(steady state condition for 'M')
ry
k_ l CO +k L
::::: kI[M-CO], (when k[L] » k_I[CO], i.e. in presence of excess L).
ra
ib
M-CO + L ~ M-CO, L or [L-M-CO] ~ M-L + CO
yl
This second-order path may originiate either from the interchange path (I) or pure associative
(A-path) (see Chapter 5, for the derivation of rate laws).
m
For the octahedral starting complex, A-path (i.e. formation of the 7-coordinate intermediate) is
relatively unlikely. However, for the tetrahedral complexes, A-path may be possible. Thus for the
he
octahedral complexes, the second-order path arises from the I-path which may be Id (i.e. bond breaking
is more important) or I a (i.e. bond formation is more important). The experimental evidences, i.e. the
lc
rate dependence on the metal-carbonyl bond strength and quite insensitiveness towards the nature of the
entering ligand indicate the Id-path.
ea
10.2.3 Dissociative Activation (D and Id ) of Substitution of CO Group
th
It has been already mentioned that for the substitution of CO group in many cases, the kI-path
(characterised by the positive values of both i1H# and i1S#) involves the D-path and the k2-path
e/
(characterised by the relatively smaller positive i1H# value and less positive i1S# val~e, compared to
t.m
those of the k1-path) involves the I d process. In some cases (as in [Ni(CO)4])' the k2-path of the two term
rate law remains almost absent (i.e. k i » k2). Examples of some reactions passing through the dissociative
activation are discussed below.
(i) [M(CO)6f + L ~ [M(CO)sL] + CO, (L = *CO, PR 3 say; M = Cr, Mo, W).
e
These hexacarbonyls of Gr. 6 experience the dissociative activation.

er
In the k1-path (i.e. D-path), the i1Hf values run in the sequence: Mo < Cr ::::: W. The order of the
M-C bond strength (measured in terms of VM-C stretching frequency; see Q.40, Chapter 9) also
H
follows the same sequence. It supports the dissociative activation as the enthalpy of activation for a
dissociative path largely depends on the metal-ligand bond strength. Interestingly, i1H{ (for the k2-path)
k
also follows the same sequence, Mo <Cr ::::: W but i1H 2# is significantly less than i1H I#. It is due to the
lic
fact that the k2-path involves the I d path where though bond breaking mainly contributes to i1H#, bond
formation by the entering nucleophile also contributes to some extent.
C
Note: For the ligand exchange reaction, [M(CO)6] + *CO ~ [M(CO)s(*CO)] + CO, the reaction
predominantly passes through the k1-path (i.e. D-path). For the ligand substitution reaction like, [M(CO)6]
+ PR 3 ~ [M(CO)s(PR3)] + CO in solvents like THF both the k i and k2-paths contribute. The solvent
may stabilise the 5-coordinate intermediate produced in D-path.
(ii) [Ni(CO)4]+L -co >[Ni(CO)3L] _+cLo )[Ni(CO)2L2]' (L=*CO, PR 3)
In these reactions, the rate law contains only the kI-term (i.e. D-path) and where i1H# (::::: 102 kJ
mol-I) is mainly controlled by the Ni-CO bond dissociation energy. The high positive value of i1S#
(32 - 35 J K- I mol-I) is also in conformity with the dissociative activation.
(iii) [M(CO)sL] + L' -----7 cis-[M(CO)4LL'] + CO,

(L = n-donor ligand or weak n-acid ligand, M = Cr, Mn, etc.)
This reaction occurs through the dissociative path and [M(CO)sL] reacts faster than [M(CO)6]. This
aspect has been discussed in Sec. 10.2.1.
10.2.4 Associative Activation of Substitution of CO Group
ry
(i) Ring slippage in "s_Cp system: The organometallic compounds maintaining the 18e-count gener-
ra
ally adopt the dissociative activation but if the rearrangement of the nonleaving ligands (e.g. lls-Cp,
NO, 116-C6H6 etc.) can produce the 16e-species, then the associative activation leading to the activated
ib
complex/intermediate of 18e count may occur. This aspect has been explained (cf Sees. 9.6.6, 10.2.1
and 5.28).
yl
[Rh(CO)2 (115-CP)J ~[Rh(CO)2 (11 3- Cp)]
m
In presence of
(18e) (16e)
the entering
[ Mn(CO)3 (115_Cp)J~[ Mn(CO)3 (11 3- CP)J
he
nucleophile (L)
(18e) (16e)
5
[ Mn (CO)3 (11 -Cp)] + L :~t~~~~:~~) [ 3 lc
Mn (CO)3 (11 -Cp)(L)] U~~) [ Mn (CO)2 (11 5-cp)L]
ea
(18e) (18e)
lls-Cp is as a 5e-donor ligand but 113-Cp is a 3e-donor ligand. By considering Cp-, lls-Cp- is a 6e donor
,,3.
th
ligand and 113-Cp- is a 4e-donor (equivalent to allyl) ligand. This "s. to slippage occurs to accom-
modate the electron pair of the approaching nucleophile (cf electromeric effct). Actually with the
e/
approach of the entering nucleophile, the metal centre moves to one side of the Cs-ring and one electron
pair is removed from the metal-ligand coordination and the electron pair is concentrated on a carbon of
t.m
the cyclopentadienyl ring. It makes the metal centre electron deficient and consequently the metal
centre attracts the nucleophile.
~ r=:1 }
e
113-CP
115-C P{
T
er
+L
~o
------t~~
Mn
Mn"" L Mn (18e)
/1'"
H
DC
CO
CO oc~1CO CO OC~I~L
CO
k
(18e) (18e) \
9- ~
lic
C
(Electromeric effect)
&--------------:~ (16e) Mn+~·L
(in presence of L) / I" .
DC CO
CO
The characteristic features of the associative activation, i. e. negative entropy of activation (~s;;t)
and rate dependence on the nature of the entering nucleophile are noticed in these reactions.
(ii) Ring slippage in ,,6_C 6H 6 system: Similar ring slippage leading to the associative reaction is
illustrated in the following reaction.
6e-donor{ ~ 4e-dOnOr{ m 2e-donor { ~

'T
Me
+L.
-------31~.
11
Me--L--~~.
+L OC~/L
Me
+L
--e-6H-6-i1~·
[(CO)]
Me L
/1" /1'"
3 3
OC/ I ~L
OC CO OC CO C
ry
CO CO 0
(18e) (18e) (18e)
ra
The above reaction experience an associative activation at each step. It is supported by negative ~s;t,
ib
steric retardation and rate dependence on the nature of the entering group.
(iii) Linear nitrosyl to bent nitrosyl: Metal nitrosyls can rearrange from NO+ (3e-donor) to NO-
yl
(Ie-donor) to accommodate the nucleophilic attack in the associative path.
m
~OJ
he
+L +
M==== N====0 -----3~
.. M-N
(18e (16e l\ .. , (cf Sec. 9.6.6)
:L
lc
ea
In fact, this associative path predominates in the metal carbonyl-nitrosyls like [Fe(C0 2)(NO)2],
[Co(CO)3(NO)], [V(CO)5(NO)], etc. These aspects have been discussed in Secs. 9.6.6 and 5.28.
[W(CO)4(NO)X] reacts in the following reactions in different paths depending on the nature of the
th
entering ~nucleophile.
e/
[W(CO)4(NO)XJ +~~~3 >[ W(CO)3 (NO)(PPh 3)X](X = halogen)

t.m
It occurs only through the dissociative path (i.e. k1-path) supported by high ~H;t and positive ~s;t
values. ~H;t
value increases in the sequence:
X = I ) Br) CI
e
As the halogen becomes larger, it becomes less electronegative and more polarisable and consequently
better 1t-donor. This better x-donor property of X will strengthen the metal --+ CO bond x-back
er
bonding. It will enhance the metal-CO bond strength and consequently W-CO bond needs more
energy for its rupture. It explains the order of ~H;t assuming the dissociative activation.
H
[W(CO)4(NO)XJ P(:~~), >[ W(CO)3(P-nBu 3)(NO)X]

k
It shows a two term rate law, i.e. kt-path (dissociative path) and k2-path (associative path). These
lic
are supported by the ~s;t values. For the kt-path, it is positive while it is negative for the k2-path. In fact,
P(n-Bu)3 is a better nucleophile than PPh 3 and this is why it can introduce the associative path (i.e.
C
k2-path) where NO is converted into NO- in the activated complex to maintain the 18e count.
(iv) Electron deficent carbonyls: 16e or 14e complexes generally adopt the associative path where
the activated complex attains the 18e or 16e-count. [V(CO)6] (a 17e-species) also responds to the
associative path where the transition state is a 1ge-complex.
Note: [Pt(C 2H 4)CI 3 ]- (l6e-species, Zeise's anion) participates in a very rapid olefin exchange
process while [(1l5-Cp)Rh(C2H4)~] (18e-species) is relatively inert to the olefin exchange process. It is
due to the fact that the 16e-species can easily respond to the associative activation while the 18e-species
fails to respond to the associative path as the corresponding transition state is a 20e-species which is
thermodynamically unstable.
10.2.5 Reactions of the Coordinated CO Ligand (cf. Sec. 10.12)

Nucleophilic attack on C: If the terminal CO group is coordinated to the metal centre which is
relatively electron deficient, then the metal d-electrons are not sufficiently delocalised towards the
carbonyl moiety (i.e. metal to CO n-back bonding is not much important). Generally, it happens so
when the metal centre is neutral or positively charged. In such cases, polarisation of the coordinated CO
may be represented as follows and it is supported by relatively higher stretching frequencies (vco) and
ry
lower stretching frequencies (v M - C).
.c
ra
8- 8+ 8- 8+
M + :C==O:~ M-C=O
ib
~:NU
yl
Strong nucleophiles (e.g. methyltithium) can attack the C-centre of such coordinated CO group. It is
m
illustrated in the following reactions.
he
lc
ea
th
~[(OC)s ~-
e/
[Mn(CO)6 t + LiCH 3 Mn - CH 3 ] + Li+

t.m
1
e
+ excess MeNH 2
er
-MeNH 3 (deprotonation)
H
k
lic
10.2.6 Nucleophilic Substitution versus Cluster Fragmentation

When the M-M bonds and M-L bonds are of comparable strength, both the ligand substitution and
C
cluster fragmentation may go on simultaneously. It is illustrated for [Fe3(CO)12]'
)[Fe 3 (CO)11(L)]+[Fe 3 (CO)lO(L)2]+ [Fe 3 (CO)4(L)]
+[ Fe(CO)3(L)2 ] + [Fe(CO)s ] + CO
However for the heavier congeners, the M-M bonds are relatively stronger and in such cases, the
substitution reaction predominates without any significant extent of cluster fragmentation.
[M 3 (CO)12] + L = PPh 3 ) [M 3 (CO)11(L)] + [M 3 (CO)lO(L)2 ],(M = Ru, Os).

10.2.7 Photochemical Reactions of Metal Carbonyls

These are discussed in Sees. 6.9.2-3.
10.3 PROPERTIES AND REACTIVITY OF FISCHER AND SCHROCK CARBENE

COMPLEXES (cf. Sec. 10.13.7)
x
ry
( 1) Synthesis of Fischer Carbene (having the M = C ( segment) bearing an electrophilic carbene
ra
R
carbon:
ib
~U+ ~-CH (~ther
yl
[ MO(CO) ] + UCH [(OC) Mo- ]-; starting materials like [Cr(CO)6], [W(CO)61,
6 3 5 3 L,Ph may be used).
m
The produced acyl compound reacts with the carbocationic reagents to produce the Fisher Carbene
he
type neutral compound which is stable and can be easily handled in the systhesis of many important
organic compounds.
Li+[(OC)n-1M-~-CH3r =1~CH3
+ R30+ BFi ------r
lcOC )n-1 M
ea
rR20+LiBF4
th
The reaction path leading to the Fisher Carbene may be represented as follows .
e/
.n/C~-
t.m
(OC)n-1 M-C ~
~(O+
e
R/ \'----R
er
(2) Nucleophilic attack on the C-centre of Fischer Carbene: Thus in the 'M=C' bond, the
H
n-bond is produced by the d-orbital of the metal centre and p-orbital of the C-centre (i.e. d-p 1t-bond).
k
~p
lic
J.::::L /OR .. +
(OC) M-C + "NH - A ' ----.. (OC)n-1M-LC-NHA
I
C
n-1 ~. 2 ~
Ph H
j -ROH
/Ph
(OC) 1M===C
n- "'NHA'
The carbon centre is attached with the electron withdrawing atom like O. The M = C bond is polarised
to generate a positive charge on the C-centre. This is why, in the Fischer carbene, nucleophiles can
attack on the electrophilic C-centre.
Thus starting from the metal carbonyl, new carbene ligands can be synthesised through the Fischer
carbene.
(3) Schrock carbene complexes: Schrock carbene complexes (having the M=CR2 linkage) of
ry
relatively higher oxidation states of the early transition metal centres are different from the Fisher
ra
carbene complexes. Schrock carbene complexes were prepared in the following reaction.
ib
/CMe3]
[M(CH2CMea)aCI2] + 2Me aCCH2Li ~ [ (Me aCCH 2)a M = C"-H
yl
(M = Ta, Nb) + CMe 4 + 2LiCI
m
The course of the reaction can be explained in terms of the intramolecular a-H abstraction by the
he
leaving group -CH2CMe3 in a cyclic transition state from an intermediate [M(CH2CMe3)5].
H"" /CMe 3
lc
ea
M/C""'-H
"""c__
th
CMe 3
e/
H2
t.m
(4) Nature of the metal-carbon bond in Fischer and Schrock carbenes: In the Schrock carbenes,
the 'M-C' bond bears the more double bonded character than that in the Fischer carbene complexes.
In the Fischer carbenes, the heteroatom (e.g. N, 0) substituents on carbene gives some double bonded
character in the C-heteroheteroatom bond. In Schrock carbenes, no such heteroatom substituent is
e
present.
er
H
~ S'x:
k
lic
M-C",
R
C
(Fischer-Carbene) (Fischer-Carbene) (Schrock-Carbene)
In the Fischer carbene, [Ph - C = Cr (CO)5]' the resonance can produce the cis- and trans- isomers
I
OCH 3
because of the hindered rotation about the C-O bond having the double bonded character. In fact, at
low temperature, the methyl protons give two PMR signals. However, at room temperature, one PMR
signal is noticed. In fact, at higher temperature, the cis- trans- interconversion rate is faster than the
NMR time scale.
Bonding in Fischer carbenes, may be explained by considering the singlet carbene ligand acting
as a 1t-acid ligand (cf the behaviour of singlet 02' Chapter 9). In Schrock carbenes, carbene is consid-
ered in the triplet state that makes an ethylenic double bond with the metal centre. These aspects will
be discussed later.
Schrock carbenes may be considered as the alkylidene complexes having the dianionic : CRi-
ligand. The lone pair (in Sp2 orbital) of C is used for a-donation and the other lone pair (in a p-orbital)
ry
is used for 1t-donation to stabilise the higher oxidation state of the metal centre.
ra
In Schrock carbenes, the bond polarity o+M= C o- indicates the nucleophilic attack on M and
electrophilic attack on C (cf the difference with the Fisher carbene).
ib
yl
m
he
R" R'
~dJ
~/ /R'
/
C
-~~ ~-r:~"
O---C lc (ct. Sec. 10.13.7, Olefin
metathesis catalysed
ea
M--C"'-R + by Schrock carbenes)
"R
th
I
e/
M=O + R'R"C=CH(R)
t.m
In Schrock carbene, the M=CH 2 linkage is comparable with the phosphonium ylids such as
Ph 3P=CH 2·
(5) Characteristic features of the Fischer and Schrock carbene complexes: In the Fischer metal
carbene complexes, :CXY (i.e. carbene or its derivative) acts as a ligand. Considering the singlet state
e
of :CXY, it may be argued that the Sp2 carbon houses a lone pair in a sp2-hybrid orbital and it is donated
er
to the metal centre. The vacant p-orbital can participate in n-bonding with the filled orbital of M, X and
Y. Thus in the Fischer carbene complexes, one or both of the carbon substituents is/are capable of
H
forming the n-bonds with the vacant p-orbital of the carbene carbon. Thus the following resonating
structures are plausible.
k
lic
00
X
- +/
C
~M--C
"'-v:
(Fischer-carbenes)
The observed metal-carbon bond length is slightly longer than the metal-CO bond length. It
supports the importance of n-bonding interaction with the carbon substituents (X, Y). The resonating
structures indicate the electrophilic character of the C-centre.
It may be noted that in the Schrock carbenes, no such n-bonding with the carbon-substituent is
possible.
(Schrock carbene)
ry
ra
202.5 pm
In Fischer carbene, if the substituents (i.e. X, Y) are very good n-donor then the carbene fails
ib
to act as an electrophile because of the following predominant structures as in the case of
[(OC)sCr = C(NR)2].
yl
m
he
lc
Here the positive charge is located on the N-centre not on the C-centre.
ea
(6) Difference in reactivities of these two carbene complexes in terms of the MO-energy diagram:
Here it is worth mentioning the properties of Schrock carbene involving the purely hydrocarbon
th
alkylidene ligands (e.g. CH 2 , CHR, CR 2 ).

e/
t.m
(Schrock carbene) (Fischer carbene)

e
In Schrock carbene, the M = C bond is polarised to develop the negative charge on the C-centre
(cf Fischer carbene where the positive charge is developed on the carbene-C atom). In fact, the difference
er
in property between these carbenes: carbene-C is electrophilic in Fischer carbenes while

carbene-C is nucleophilic in Schrock carbene, can be better understood in terms of the MO energy
H
LUMO "LUMO \~
k
('AI~,
"" ~\ \ ..
lic
•• I , C( )
Nu: '~ ~" \ Nu
I I
I I M (d) " \ \
C
I I \
I I \ \
\ \
I I
~
I I \ \C(pz)
I I + \ \~
~ ~E+ E \ I~
(a) \ / i \
\ I
I
\ I
M(d) " I
~ \--4b- 1
HOMO HOMO
(b) Fischer carbene (c) Schrock carbene
Fig. 10.3.1 (a) d-p overlapping interaction in the carbene complexes, (b) Simplified MO energy diagram in Fischer
carbene; (c) Simplified MO energy diagram in Schrock carbene. (Nu = nucleophile; E+ = electrophile).
diagram. Nucleophile (Nu) attacks on the LUMO which is enriched with the orbital of carbene carbon
for the Fischer carbenes while for the Schrock carbenes, the LUMO is enriched with the orbtals of the
metal centre.
Fischer Carbene vs. Schrock Carbene (Summary)

• Free carbenes (i.e. CH 2, CR 2) can exist in both singlet and triplet states. In triplet carbene,
ry
there are two unpaired electrons while in singlet carbene, there is no unpaired electron.
ra
ib
yl
m
he
(Singlet) (Triplet)
In both cases, the C-centre is sp2-hybridised. In singlet carbene, the pure p-orbital (say pz) is
lc
vacant while in triplet carbene both the unutilised sp2-orbital and p-orbital bear an unpaired
electron each.
ea
• In Fischer carbenes, bearing a heteroatom (e.g. 0, N) substituent on the carbene carbon, the
singlet form is the predominant one. Such singlet carbenes can act as the 1t-acid ligand (cf.
th
singlet O2 as a n-acid ligand). They can donate the lone pair housed in the sp2-hybrid orbital and
receive back electrons in the vacant p-orbital. Here there is a competition between the heteroatom
e/
substituent of carbene and the metal centre for n-bonding with the vacant p-orbital of the carbene.
Because ofthis competition, the 'M - C' bond is too long for a M - C double bond. Here it may
t.m
be mentioned that the metal-carbene n-bonding may be further weakened due to the presence of
other auxiliary n-accepting ligands bound with the metal centre.
e
er
H
k
lic
• In Schrock carbene, the carbenes exist in triplet states. The two unpaired electrons partici-
pate in bonding to give the M-C double bond (ef ethylinic double bond).
C
• In Fischer carbene, the carbene-C centre is an electrophile while in Schrock carbene, the
carbon centre is a nucleophile.
In Fischer carbenes, the d-orbital of the metal centre is of relatively lower energy compared to that
of the Schrock carbene. In Fischer carbene, HOMO is enriched with the character of the d-orbital of
metal centre and LUMO is close to the atomic orbital of carbene carbon. On the other hand, in Schrock
carbene, the reverse is true. Thus in Fischer carbene, the carbene C-entre is electrophilic and in
Schrock carbene, the carbene C-centre is nucleophilic (ef Fig. 10.3.1).
A nucleophile attacks on the LUMO. This is why, nucleophilic attack occurs on the C-centre in
ry
Fischer carbene while the nucleophilic attack occurs on the M-centre in Schrock carbene.
Reaction of a Schrock carbene with an electrophile like (CH3)3Si-Br is shown below with the
ra
M=C bond polarisation.
~Si('\Br
ib
(llS-Cp)2Ta===CH 2 _
yl
I -Br
m
CH 3
he
lc
ea
(7) Application of Schrock carbenes: Tebbe's reagent shown below is actually a Schrock carbene
th
and it is the functional equivalent of (CP)2Ti=CH 2.

e/
. -CH 4 . /CH 2" , _ .

CP2T1Me2 + AIMe2CI • (ljS-GP)2T1"""CI/ AIMe2= (ljLCp)2T1=CH2 + AIMe2CI
t.m
Tebbe's reagent can be used to transfer the 'CH 2' group (cf oxophilicity of Ti(IV)).
R [0 R] -CP2 TiO
e
R)C=O Tebbe's reagent ) CP2Ti*R

er
[ef R2C=O + H2C=PR; (phosphonium ylid) ~ R2C=CH2 + R;PO, Wittig Reaction, see Vol. 2]
H
Carbenes can be used to produce the cyclopropane derivatives.

k
-CH [(*Cp)Fe(CO)=CHMe] H" A. /H

lic
Ph CH - 2 ... ~ ;*Cp=CsMes
Me Ph
C
These carbenes are very much similar to Wittig reagent Ph 3P=CH2.

See Sec. 10.13.7 for the olefin metathesis catalysed by Schrock type carbenes.
(8) Carbyne or alkylidyne complex: From Fisher carbene, carbyne complex was prepared first.
.0
(OC)sW==C,
PSGI, ~
+
[(OC)sW==CMe] BCI:; + BCI 2 (OMe)
OC", /CO
CI-W==C-Me
Me 1
-co OC/ "'co
trans-[ CI(OC)4 W==CMe] + BCI 3
Here the Lewis acid BX 3 attacks the O-site of the carbene. The intermediate loses CO and the halide
coordinates at the trans-position to the carbyne linkage.
In fact, this route has been applied to synthesise many other carbyne complexes.
OMe
(OC) M C/ Lewis acid )[X(OC)4 M ==CR]+CO+SX 2(OMe)orAIX 2(OMe)
5 = '\ (BX 3 or AIX 3 )
R
ry
M = Cr, Mo, W; R = Me, Et, Ph; X = CI, Sr
ra
The carbyne or alkylidyne complex may be obtained through the deprotonation of alkylindene or
carbene complex. f)
ib
(Me3CCH2)3Tav=c,\
0 H
B L"+
u- I )Li+
[
(Me3CCH2)3Tav==CCMe3
J- +C4H1Q.
yl
CMe 3
..
m
The monohapto carbyne ligand (oCR) is a 3e-donor ligand (cf NO). The lone pair housed in a
sp-hybrid orbital can be used for a-donation; the unpaired electron in a pure p-orbital participates in
he
n-bonding; the vacant p-orbital can receive back electrons through n-bonding from the metal centre. It
gives the M-C triple bond.
lc
~Q
ea
R-C<::::j1) + M---+ R-C=:M
dO
th
e/
t.m
Gradual removal of H-atom from CH 4 gives methyl, carbene, carbyne and atomic C successively.
All these can act as the ligands. The complexes bearing the atomic carbon as the ligands are described
as the carbido complexes (e.g. [Fe6C(CO)16]2-).
e
er
Typical W(VI) complexes containing M-C, M=C and M==C bonds.

H
W-C = 225.8 pm
k
W==C = 194.3 pm
lic
W=::::.C= 178.5 pm
C
10.4 METAL CARBONYLS AS NUCLEOPHILES AND BRONSTED BASES (ct. Secs. 9.4.7E,
9.4.17,10.1)
Several metal carbonyls as anions can act as the nucleophiles. Examples are:
[(Cp)Fe(CO)~- ) [(Cp)Ru(CO)~- ) [(Cp)W(CO)~- ) [Mn(CO)~- ) [(Cp)Mo(CO)~- ) [(Cp)Cr(CO)3]-
) [CO(CO)4]- (arranged in the order of relative nucleophilicity).
The said anionic metal carbonyls may be considered as the bases. In fact, on combination with H+,
they can form the conjugate Bronsted acids. The examples are:
[HMnCOs], [HCO(CO)4]' [H2Fe(CO)4], etc.
Generally, their acid strength increases on moving from left to right along the period. Strikingly, on
protonation, their structure changes, i.e. the conjugate acids and bases are of different structures.
It is illustrated below. In this structural change, a metal-CO n-bonding pair is converted into a
ry
metal-H+ a-bonding pair.
ra
CO
CO
I oc""'- I
ib
Fe + /Fe-co
I""'-co
yl
OC/
CO
OC I
H
m
(18e) (18e)
he
r
Their behaviour as the nucleophiles can lead to the formation of a new metal-carbon bond.
[Fe(CO)4t + RX-------)[R-Fe(CO)4T + X-;[R-Fe(CO)4T (in:e~~n) >[R- -Fe(CO)4

lc g
ea
th
e/
• Use of Na2[Fe(CO)4] known as Collman's Reagent (described as the Transition Metal

t.m
Grignard Reagent) in Organic synthesis: See Sec. 9.4.17.

• Na[Co(CO)4] also finds uses in organic synthesis (see Sec. 9.4.17).
e
[Mn(CO)s]- + CICH 2CH=CH 2 ~[(OC)sMn-CH2CH=CH2J + cr

er
CH3CO-CI~[ ~-Fe(CO)2(T]5_CP)]
H
[Fe(CO)2(T]5 -Cp)r + CH 3 -
k
[Mo(CO)3(l1S-CP)]- +R-CI~[(l1S-CP)(CO)3 Mo-R]

lic
[CO(CO)4]- ~[R-CO(CO)4] (" +Crt~ )[R-C-CO(CO)4]~RCOOR'+[HCO(CO)4]

-x
)
II
C
tnse Ion
o
This property may be utilised for the formation of metal-metal bond on also.
[(115-CP)(OC)3MO r + Ph 3Sn-C1 -Cl- >[(115_Cp)(OC)3Mo-SnPh3]
[Fe(CO)4]2- + Hg 2+ ~ [HgFe(CO)4]
Fe(CO)4]2- + 2Ph3PAuCI ~ [(Ph3PAu)2Fe(CO)4] + 2CI-
[CO(CO)4]- + [Mn(CO)sBr] ~ [(OC)4CoMn(CO)4] + Br-
Note: Metal basicity and nucleophilicity generally increases for the heavier congeners in a group, e.g.
[(Cp)W(CO)~- ) [(Cp)Mo(CO)~- ) [(Cp)Cr(CO)~- (cf. Sec. 9.4.7E)
Exception (in Fe-group): [(Cp)Fe(CO)2]- ) [(Cp)RU(CO)2]-
Replacement ofa stronger n-acid ligand by a weaker n-acid ligand enhances the electron density on
the metal centre because of the less efficient metal ~ ligand pi-back bonding. Consequently,
ry
mucleophilicity and basicity increase. Thus replacement of CO (probabily the strongest n-acid-ligand)
by the relatively weaker n-acid ligands like PR 3 , lls-Cp enhances the nucleophilicity and basicity.
ra
In the anionic hydrido carbonyls, e.g. [HM(CO)s]- (M = Cr, W), [HFe(CO)4]-' etc., the hydrogen
is of hydridic character rather than of protonic character. It may be noted that in the neutral carbonyl
ib
hydrides, the hydrogen is of protonic character rather than of hydridic character. In fact, the anionic
yl
hydrido caronyls can act as the hydride donors:
m
he
[HFe(CO)4]- + RCOCI~RCH + [CIFe(CO)4]-
II
o lc
ea
10.5 INSERTION AND DEINSERTION REACTION
Small molecules like A-B (e.g. CO, etc.) may be inserted into the metal-ligand (M-L) bonds, spe-
th
cially the M-C and M-H bonds. These are of two types:
e/
(i) M-L+A-B~M-A-L; (1, I-insertion)

I
t.m
B
(ii) M-L + A-B ~ M-A-B-L; (1, 2-insertion)
The reverse reactions of insertion reactions are called deinsertion or extrusion or simply elimination.
e
The insertion reactions involve the insertion of CO, S02 and olefins.
er
The name of insertion reaction arises from the result of the reaction like:
M-L+ :X~M-X-L
H
The name may be misleading from the standpoint of mechanistic paths. In terms of the mechanistic
path, the reaction can be described as the ligand migration reaction.
k
lic
10.5.1 Characteristics of CO Insertion: Carbonylation and Decarbonylation Reactions

The CO-insertion reaction is known as carbonylation. It is illustrated in the following example involv-
C
ing pentacarboylmethylmanganese.
[H 3 C-Mn(CO)s] + CO ~ [H 3 C-C-Mn(co)s] ; (C-bonded ,,1- acety l; sometimes, the oxophilic

II centre bears the C- and 0- bonded ,,2-
acetyl).
o
To explore the mechanistic paths of the above mentioned reaction, several studies have been carried
out.
From the isotope labeling experiment, it is found that the 'CO' group inserted comes from the
CO-groups already coordinated.
[H 3C - Mn(CO)s] + 'CO ----7 [H 3C - ~- Mn(CO)4 ('CO)]
Thus in general, the said insertion reaction may be represented as follows in general.
[H 3C-Mn(CO)s] + L----7[H3C-~-Mn(CO)4L]
ry
(L = CO, amines, phosphines)
ra
For the so called CO-inseration (i.e. carbonylation) reaction, the rate process shows a first-order
ib
dependence on [CH 3Mn(CO)s] and a first-order dependence on *CO. It indicates that the nucleophilic
attack by 'CO is quite imporant also. It suggests the following rearrangement.
yl
H3 C,
m
I "
I
--~.. : ' .. Mn(CO)4 --~•• Product
: ........ I
he
O===C *CO
lc
(a) Rate law: The rate data have been explained in terms of a two-stage mechanism outlined below.
ea
R-Mn(CO)4], :1 > [M n(CO)4],
2
k (+L) , [L - Mn(CO)4]; (L = CO, amines, phosphines)
[ I -1
1
C=O
k_ 2 (-L)
ci
I a RCa (acylgroup)
th
CO I
R MeCO (acetyl group)
R
(NVE = 18) (NVE = 16) (NVE = 18)
e/
(Octahedral) Trigonal (Octahedral)

bipyramidal
t.m
The intermediate (NVE = 16) may coordinate with a solvent molecule to attain the 18e count. Here
the first step represents the R-migration or alkyl migration.
Under the steady state condition for the concentration of the intermediate species (I, say), the
e
following rate equation arises:

er
d[I]
---:it = 0 = k1 [Complex] - k_ 1 [I] - kz [I][L] + k-z [Productl
H
[I] = k1 [Complex] + k_z[Product]

k
i.e.
k_ 1 + k 2 [L]
lic
Rate =kz[L] [I] - k_z[Productl = kz[L]

k 1 [Complex] + k
t ]
[Product]
- k_ z [Productl
C
k_ +k
1 2 L
Considering the completion of reactions (i. e. k_ 2 is negligible), the observed first order rate constant
can be expressed as follows:
k obs = k 1k Z [L] ( k ) .
[ ] == _1 k 2 [L], (at very low concentratIon ofL)
k_ 1 + k 2 L k_ 1
= K eq k 2 [L).
and, kobs ::::: k b (at very high [L]).

The above rate equation can be rearranged as follows:
-1- - - 1 J+-
k_}- ( -- 1
kobs - k}k 2 [L] k}
The double reciprocal plot, i.e. -1- vs. -1[] gives a finite intercept (= 11k,) and slope ( = kk_k )
l
•
ry
k obs L } 2
For the different entering ligands, the slope changes but the intercept remains unchanged. It is
ra
due to the fact that k I (cf intercept = l/k I ) depends on the nature of the starting complex but not on the
nature of the entering ligand (L). The kI-step produces the acetyl complex through the migration of the
ib
Me-group (i.e. R = Me).
(b) Stereochemistry of the carbonylation and decarbonylation reaction: The findings are:
yl
(i) [CH 3 Mn(CO)s] + *CO~Only cis-[CH s COMn(CO)4(*CO)]
m
he
CH 3
CH s I
c===o
OC~I/CO OC'~I/CO lc
i.e. Mn + *CO -----:l~~ Mn (Carbonylation)
ea
oc/I~co
co oc/I~co
co
th
(cis-product)
e/
CH 3
I
t.m
*c===o CH s
oC~I/cO oC~I/cO
(ii) Heating
/MI~
Mn ~
+CO (Decarbonylation)
e
oc/I~co
er
CO
oc CO
CO
H
(cis-product)
In the carbonylation reaction (i), existence of no tagged CO in the acetyl group supports the intra-
k
molecular path and rules out the direct insertion ofgaseous co into the M-R bond. The exclusive cis-
lic
product in carbonylation indicates the product as the kinetically controlled product (cf the trans-
product is expected to be thermodynamically more stable, on steric ground when the entering ligand is
C
bulkier than CO). The stereoselectivity of the decarbonylation process again is also expected from
the principle of microscopic reversibility.
The above stereoselectivity in the carbonylation and decarbonylation process however cannot dis-
tinguish between the CO insertion and methyl migration paths because both the paths will lead to the
same product.
~ M- ~- CH s (Carbonyl insertion)
o
10
ORGANOMETALLIC REACTIONS AND THE REACTION PATHWAYS: REACTIVITY OF COORDINATED LIGANDS: CATALYSIS
CO
H3 ------:l~~ r
C=O
(Methyl migration)
1523
I
CH 3
ry
(c) Carbonyl insertion vs. methyl migration: To distinguish between these two possible pathways,
ra
definitive stereochemical analysis of the decarbonylation reaction (i.e. reverse of carbonylation) has
been carried out. These are illustrated for decarbonylation ofcis-[CH 3COMn(CO)4(*CO)].
ib
(d) Decarbonylation reaction through the CO-insertion pathway:
yl
CH 3
I
m
c=o
IBO \/CO CH
he
-*CO
OC--Mn-CO
oc/I
.~
------:l
(1-path)
.
/1
OC--Mn-CO
lc (to 1-cis-position)
OC CO
ea
CO
(25% probability)
th
e/
CH
l)cO
t.m
-co
------:l~~ 0\.1 --Mn-CO (to remaining 3-cis-positions)
(3-paths) / I
OC
e
CO
(75% probability)
er
(CH 3 and *CO in cis-positions)

H
In the carbonyl insertion pathway, the CO group of acetyl ligand has 4 choices for the equivalent
cis-positions. One path leads to replacement of *CO while the other three paths lead to the replacement
k
of nontagged CO groups. This will lead to 25% product bearing no *CO and 75% product bearing the
lic
:0 group. This prediction is not satisfied with the experimental findings discussed later.
(e) Methyl migration pathway
C
r3~ co
17~-.co I/CH 3
OC
/ 1
OC--Mn--CO ------:l~~
(1-path)
OC
/1
OC--Mn-CO
CO CO
(25% probability)
o
*CO
-co
(*CO and CH 3 in cis-positions)
ry
2 possible orientations
ra
co
(50% probability)
ib
yl
m
he
OC co
oc I/*CO
-co lc ~
-~ ""Mn (*CO and CH 3 in trans-positions)
/I~co
ea
H3 C CO
th
(25% probability)
e/
The methyl group transfer to the equivalent 4-cis-positions can occur in 4-ways. It will lead to
t.m
following product distribution.

25% (product bearing no *CO), 25% (*CO and CH 3 in trans-positions), 50% (*CO and CH 3 in cis-
positions). The experimental findings are in conformity with the methyl group transfer pathway.
e
(f) Ca~bonylation and decarbonylation in the optically active tetrahedral complexes: The
er
decarbonylation mechanism outlined above can also be proved by considering the tetrahedral (better
pseudotetrahedral) chiral complex of iron, [(1l5-Cp)Fe(CO)(COEt)(PPh 3 )].
H
llS-r llS-r
k
lic
hv
Fe Fe + *CO
/I~/El
O/I~EI
C
Ph P C
3 OC· II PPh 3
o
(Inversion of configuration)
CO insertion leads to retention of configuration and it is not supported experimentally. The inversion
of configuration can be explained by considering the migration of the Et-group to the coordination site
vacated by the *CO group. The reverse reaction, i.e. carbonylation reaction also leads to inversion as
expected from the principle of microscopic reversibility.
115-Cp
+CO insertion
~ Fe
+'CO
-----:J~~
I
Fe
(a)
Ph3( 0"'1=0 Ph3!.l~CI =0
ry
Et
Et
ra
(Retention of configuration)
ib
yl
Alkyl migration +*CO
(b)
m
he
(Inversion of configuration)
lc
(g) Conclusion· mechanistic aspects of carbonylation and decarbonylation: In the decarbonylation
ea
of metal bound acyl group (ReO), the alkyl group (R) migrates to a coordination site vacated by a
ligand, generally CO. Thus it is reasonable to conclude for the reverse carbonylation reaction that the
alkyl group migrates to an adjacent metal bound CO group and the site vacated by the alkyl group is
th
occupied by a new ligand like CO or phosphine.

e/
Thus the so called CO-insertion reactions are basically the alkyl migration reactions.
Thus the carbonylation reaction may be outlined as follows:
t.m
e
er
a cis-CO group
H
k
lic
CO
OC I/CO
~M
C
+ +
/In~ ~O
OC CO
CO I
CH 3
25% 50%
(*CO and COCH 3 in trans-positions) (*CO and COCH 3 in cis-positions)
( )
V
Stereochemistry of the products
(h) Rate dependence on the nature of the alkyl group in carbonylation reaction: It needs the
migration of an alkyl group. The stronger metal-carbon bond will disfavour the process more. It is
illustrated from the following rate sequence:
R = C3H7 -- C2Hs ) C6Hs ) CH 3 ) C6HsCH 2 -- CF 3.
Migration of the alkyl group probably occurs in a concerted process, i.e. the alkyl group is never
ry
free.
(i) Thermodynamic aspects of cabonylation reaction:
ra
o
ib
II
[H 3C-Mn(CO)5] + CO~[H3C-C-Mn(CO)5]
yl
~H = - 54 ± 8 kJ mol-I.
m
Thus the reaction experiences an enthalpic favour. However, it experiences an entropic disfavour
he
because it leads to fixation of gaseous CO into a complex. The origin of the enthalpic favour arises from
the following changes:
breaking of metal-carbon bond, formation of a carbon-carbon bond and formation of a new metal-
lc
carbonyl bond.
ea
The energy required to break down the M-R bond is less than the energy released by the M-CO
and C-C bond formations. This thermodynamic favour can overweigh the entropic disfavour.
th
(i) Oxophilicity of the hard and electropositive early d- and f- block elements: Because of the
affinity for 0, such hard metal centres give the C- and 0- bonded 112-acyl complex instead of the
e/
C-bonded 11 I-acyl complex formed by the late d-metals.
/o~
t.m
(11 5-Cp)2 ZrMe2 + CO~(,,5 -Cp)2(Me)Zr - C- CH 3, (,,2- acetyl)

e
10.5.2 Olefin Insertion and p-Elimination

er
Olefin insertion into the M-H (i.e. metal-hydrogen) bond is very much important (cf catalytic hydro-
genation of olefins and hydroformylation reaction).
H
M-H + R2C=CR2 ~ M-CR2-CR2H.

Olefin insertion may also occur into the M-R (i.e. metal-alkyl) bonds (cf Ziegler-Natta Catalysis
k
in polymerisation of ethylene).-
lic
M-R' + R2C=CR2 ~ M-CR 2-CR2-R'.

C
(a) Mechanism of olefin insertion: At the first step, olefin coordinates the metal centre which is
coordinatively unsaturated. Then insertion of olefin into the M-R bond (R = alkyl group or H) occurs
through a cyclic, planar, four-centre transition state.
&-
R M---,- ~
+X
I ~
M-R
>=k "'~~-- ~ (Metallacyclo-butane)
(NVE = 16) (1l2-olefin)

/ a ~'"
(NVE = 18) (A)
1~
M
'" C
I - C/R-
ry
/ a p",
ra
(NVE = 16)
ib
• In the cyclic transition state, there is a development of partial positive charge on the ~-carbon and
R group migrates as an anion (i.e. hydride or carbanion) to the ~-C centre.
yl
• In the cyclic transition state, M and R (migrating group) add in a cis-fashion to the olefin.
m
• Migration of H (as hydride) to the f3-carbon is much favoured than the migration of R (as
carbanion). It is due to the fact that the nondirectional s-orbital of the migrating H can overlap better
he
than the directional sp3-hybrid orbital of the migrating alkyl group with the orbital of ~-C.,··..
• The ease of insertion also depends on the M-R bond strength. The ease of olefin insertt'on follows
the sequence: lc
R = H » CH2(CH2)nCH3 (n ~ 2) ~ CH 2CH 2CH3 ) CH 3 ) CH 2CH 3•
ea
Among the alkyl groups, olefin insertion is disfavoured most for R = ethyl group. It is believed
that the electrons of the C-H bond (of Et-group) participates in the agostic interaction with the
th
coordinatively unsaturated metal centre. This type of agostic interaction is not possible for the bulkier
alkyl group (e.g. propyl, butyl, etc.). C-H bond of the Me-group cannot also participate in the said
e/
agostic interaction because it will produce a 3-membered ring that remains in' a strain.
t.m
Note: 1, 2-Addition to the Double Bond

LnM-X + A=B ~ LnM-A-B-X
It may be also described as the insertion of A=B into the M-X bond. In general, A=B may
e
represent different species like alkene, alkyne, carbon dioxide (ef RMgX + CO 2), ketonic com-
pounds (ef RMgX + ketone), cyanides, etc. The general mechanistic steps are:
er
A A
H
LnM-X + II -~. LnM-11 ~ LnM-A

BIB I I
!
k
X X---·B
lic
(TJ2-mode)
C
LnM-A-B-X
The first step involves the 112-coordination of A=B to the metal centre followed by the migra-
tion of X to the substrate through a four membered cyclic transition state.
(b) Characteristics of p-elimination: The reverse reaction of olefin inseration into the M-H bond
is an example of ~-elimination.
The reaction proceeds through the same cyclic (4-membered) transition state proposed for the
olefin insertion.
P H H R
8-~--/--_-CHR
~ b+ 'I
I 'C/
M-CH 2CH 2 - R - - - M---~H2 -----J.~ M-II
ry
/C"'"
H H
ra
• Thus the reaction describes the p-hydride elimination.
• It is evident that for the formation of the said cyclic transition state through the ~- H, the metal
ib
centre must have a vacant coordination site (i.e. coordinatively unsaturated). Thus the 18e metal
yl
alkyl complex like [(115-Cp)Fe(CO)2(C2Hs)] is resistant to p-hydride elimination.
• Obviously, absence of ~-H cannot cause such ~-elimination.
m
• If the substituent on ~-C is electron withdrawing, then development of negative charge on ~-H is
disfavoured and conseqll~~tly the migration of ~- H as H- will be disfavoured.
he
(c) Application of th~.olefin insertion and ~-eliminationreactions: Rh(I)-catalysed hydrogenation
of olefin involves the' olefin insertion. At the first step, the 16e species [RhCI(H)2L2] is produced
lc
through the oxidative addition of H 2 to [RhCG.. . 3] (16e species) followed by the elimination of one
L (= PPh 3 ). Then olefin insertion into the Rh-H bond of [RhCI(H)2L2] followed by reductive elimination
ea
leads to hydrogenation of olefin (Sec. 10.13.3).
Polymerisation of ethylene, catalysed by Ziegler-Natta catalysts involves the insertion of ethylene
th
into the M-alkyl bond. ".

R-
e/
------I
•• Ti
t.m
e
er
(Coordination sites around Ti not shown)

H
The following reaction is quite important in connection with the p-elimination process.
[Fe(CO)5] + 20H- ---7 HCOi + [HFe(CO)4]-'
k
The probable mechanistic path involves the ~-elimination.

lic
,I l-
C
~-
CO
OC" 1
'" F e - c* _ O + OH •
/ 1 U (Nucleophilic
attack)
.~
------I . Fe-H
/1CO
+ *C0 2
OC
CO 2 + OH - ~ HC0 3-
(ct. Water gas shift reaction)
Note: a-Elimination, a-H abstraction (cf Sec. 10.9): When ~-hydrogens are absent and bulky ligands
are present to hinder the formation of 4-membered cyclic planar transition state required for ~-elimination,
the situation may lead to intramolecular abstraction of a-H. This has been illustrated for the synthesis
of Schrock carbene complexes (Sec. 10.3). Decomposition of permethyls (e.g. WMe6' TaMes, ReMe6
etc.) to release methane occurs also through a cyclic transition state involving a-H abstraction.
WMe6 ---7 3CH4 + "W(CH 2)3'
ry
ra
ib
10.5.3 502 Insertion into the Metal-Carbon Bond
yl
The examples are:
m
o 0
R- Hg(OAc)
8°2
.~ ~s~
he
/'"
-------"l .
R Hg-OAc
lc
ea
2
[(1l5-CP)(CO)2 Fe---R ] +80 ) [(1l5-Cp)(CO)2 Fe-S0 2-R]
(R = CH 2 CH=CHPh).
th
S02 inserts directly into the M - C bond to produce an S-sulfinate. The Lewis acid S02 (isoelectronic
with SnCl 2 in terms of valence shell) directly attacks the alkyl group not the metal centre. This is why,
e/
more electron rich C-centre experiences this attack more easily.

t.m
R' R"
0+ \
M- - - -C- - - - s
/ /0
e
I ~O
er
j
j
H
o R'
II /
k
lic
M-O-~-CRRIR" ~ M-~-C\R"
o
C
0 R
In the proposed mechanism, S02 (as a Lewis acid) experiences the nucleophilic attack by the
C-centre (of the alkyl ligand) and this leads to an inversion of configuration at the C-centre.
10.6 OXIDATIVE ADDITION OR OXAD REACTION

10.6.1 General Aspects of Oxidative Addition
• Coordinatively unsaturated lower valent transition metal complexes sometimes may combine
XY to increase the coordination number by two with a simultaneous 2e-oxidation of the metal centre
(e.g. + 1 to +3).
IX
L 4 M +X-Y( )L 4 M\
(16e) y
(18e)
The forward reaction is the oxidative addition while the backward reaction is described as the
reductive elimination. In other words, oxidative addition results from the insertion afthe metal complex
ry
into the X-V bond. Here ML4 represents the square planar complex of £is-configuration and X-Y
stands for the species like X2 (halogen), H2, H-X, R-X (alkyl halide), RCO-X, etc.
ra
• The square planar complexes of the d8 system (e.g. Rh+, Ir+, Pd 2+, Pt2+) and trigonal planar
complexes of dID systems (e.g. Pdo, Pto) of the platinum nzetals obeying the 16e rule are prone to
ib
experience the oxidative addition.
yl
Examples:
m
oxidative
(i) [PtCI 4 ]2- + CI 2 ) [PtCI 6 ]2-
he
addition
(16e,+2) (18e, +4)
(ii)
/L CI'I/H
'"
Llc
ea
CI",
L/
Ir
"CO~(OXidativeaddition)
~
OC
/Ir
!
"H
th
Hel III
[Ir (CO)CI 2 HL2]
e/
(18e, +3)
t.m
(oxidative addition)
e
Starting complex called Vaska's complex (18e, +3)

er
(L = PPh 3 )
H
L
(iii) L~ /CO I~I/co
k
+Mel
Rh Rh
CI/ ~L CI/I ~Me
lic
(oxidative addition)
(16e, +1) L
C
(18e, +3)
Me-migration
(16e, +3)
Model complexes (d 8 ) of Gr. 8,9,10 for oxidative addition (L =PPh 3)

L L
I/co I/co
OC--Ru oC--Os
ry
(tbp)
I"'-co I""'co
ra
L L
ib
L~ /"CI L~ CI
yl
Rh 1/ (square
L/ ""L oc/ r"",- L planar)
m
he
Wilkinson's catalyst Vaska's Complex
H3C~ /NO CI""

lc ............. PEt3
ea
(square
H3C
/Pd""
NO Et3 p/
Pt
""H planar)
th
l-
e/
I CO
~Rh/ (square
t.m
/ "" planar)
1 CO
e
L
er
CI L 0
(iv)
+RCOCI, (-N 2 ) ~I II R-migrati r .,
CI~I/co
H
-----'""""3~. Ir-C-R Rh
I ~
CI/I~R
Oxidative addition /
and dissociation
k
of N2 CI L
L
lic
(16e, +1) .
(16e, +3)
(18e, +3)
C
Here at the first-step, oxidative addition followed by the dissociation of a ligand maintains the 16e
count though there is a 2e oxidation at the metal centre.
• Oxidative adduct formation by Vaska's complex (cf L. Vaska, Acc. Chern. Res., 9, 175. 1976;
MJ. Burk et. aI, J. A/n. Chern. Soc., 110,5034, 1988): The four coordinate 16e Vaska's complexes
trans-[Ir(CO)(PPh3)2X] (X = CI, Br, I) have been extensively studied to understand the process of
oxidation addition. The degree of oxidation of Ir is indicated by the increase of vco value. The
higher oxidation state of Ir disfavours more the Ir~CO n-back bonding and it makes the veo value
higher. It is illustrated for the complex, [Ir(CO)(Cl)(PPh3)2], simply denoted by [Ir(A 4)].
Incoming Adduct
ligand
Free complex 1967
[lr(A 4)(1l2-0 2)] 2015
[Ir(A 4)(D h] 2035
ry
HC) [H-Ir(A 4)-Cl] 2045
CH~I [H 3C-Ir(A4)-I] 2047
ra
C 2F -l [Ir( A 4)(1l2-C 2F4)] 2052
C 2(CN)-l [lr(A-l) {1l2-C 2(CN)4} ] 2057
ib
[Br-Ir(A 4 )-Br] 2072
yl
[CI-Ir(A 4 )-CI] 2076
m
• Characteristic features of the oxidative addition to the Vaska's complex:
he
(a) The higher v co value in the adduct indicates the more irreversibility of the adduct formation
process and the higher oxidation state of Ir in the adduct (cf addition of O 2 is a reversible process
while addition of Cl 2 is an irreversible process). lc
ea
(b) [Ir(CO)X(PPh 3)J + CO~[Ir(CO)2X(PPh3)J(tbPstructure)
Stability order of the adduct: X = I ) CI; Ir ~ CO n-back bonding is more favoured for X = I which
th
is less electronegative, i.e. more electron pushing.

(c) For X = I and cn3, O 2 binds irreversibly (ef I and CH 3 are more electron pushing than CI).
e/
(d) Oxidative addition of X-Y gives two new bonds, i.e. Ir-X and Ir-Y, with the rupture of X-Y
t.m
bond. This can give three possible isomers (keeping two PPh 3 ligands at the trans-positions in most
of the cases). There rnay be more 6 isomers keeping the 2 PPh 3 ligands at the cis-positions. However,
these are the minor isomers. Among the three major isomers (2 PPh 3 ligands at the trans-positions),
very often the isomer having the trans-addition of X and Y is the kinetically controlled predominant
e
product. These isomers can be identified by considering the VIr- CI values. Addition of Cl 2 gives the
er
product showing VIr- CI ::::: 300-310 cm- I (CI trans to CO) while addition of CH 3CI gives the product
showillg VIr- C1 ::::: 305 cm- I (CI trans to CO) and 260 cm- I (CI trans to Me). Addition of CH 3I gives the
H
product that shows only one band for VIr- C1 :::: 300 cm- I (i.e. CI trans to CO). The higher ir-stretching
j
trans- [lr(CO)CI(L)2l (L = PPh 3 )
k
Vaska's complex
lic
+ x-Y (leading to 3 major isomers keeping

2L at the trans-positions)
C
I I
L L L
OC"", I/ CI CI"", I/ CO X "I /
" /~
CI - 300 em- 1
./ v Ir-CI-
/Ir~ /Ir"" /Ir~

X I y X I y OC I y
L L L
V 1r- C1 ~
260 em -1 (kinetically controlled
(for Y = Me) product)
ORGANOMETALLIC REACTIOt-,iS AND THE REACTION PATHWAYS: REACTIVITY OF COORDINATED LIGANDS: CATALYSIS 1533
frequency of the Ir-CI bond trans to CO is due to the enhanced 1t-donor property of CI for the
strong 1t-acceptor CO group at the trans-position (cf Fig. 10.2.1.1).
(e) Olefins like C 2F4, C 2(CN)4 and O 2 coordinate in the adduct in the 112-mode to give the trigonal
bipyramidal structure where the 1t-acceptor ligands preferably occupy the equatorial positions. To
avoid the competition in 1t-bonding, the strongest 1t-acceptor ligand occupying one equatorial position
prefers the weaker 1t-acceptor ligands and good a-donor ligands at the remaining equatorial positions.
ry
In the 02-adduct, 112-02' CI and CO are at the equatorial positions (i.e. PPh 3 groups along the axial
directions) while in the olefin adduct, 112-C 2X 4 (X = F, CN) and two PPh 3 ligands occupy the equatorial
ra
positions. This structural difference can be rationalized by considering the 1t-acceptor strength of the
ligands: 112-C 2X 4 (X = F, CN) ) CO ) PPh 3 ) 112-02.
ib
Structures of the olefin adduct and dioxygen adduct with the Vaska's complex are shown later.
yl
(0 [Ir{A 4)J+S02 ~[Ir{A4)-S02J, (V eo ,=2020em- 1)
m
[Ir{A 4)J+ BFJ ~[Ir{A4)-BFJJ, (V eo '=2067 em-I)
he
Addition of S02 is reversible but addition of BF 3 is almost irreversible and oxidation state of Ir in
the BF3 adduct is almost +3. lc
• d 10 systems being coordinatively unsaturated can experience also the oxidative addition. It is
ea
illustrated for Pte
th
H H H H PPh 3
'-
I
I/CH3 ~ /PPh 3
e/
Pt
/PPh 3
+ Mel
.. Pt
-C 2 H4
.. Pt
"- PPh
"I
t.m
H H
3
I H3 C /"'" PPh 3
H H PPh 3
as =0) (16e, as = +2)
(1l2-C 2H4 )(16e, (1 ge, os = +2)
e
er
• The 18e complex [Fe(CO)s] can experience the oxidative addition with the loss of a CO group.
[Fe(CO)s] (18e)+1 2 ~cis-[Fe(CO)412J+CO

H
The above reaction probably occurs in two steps as follows:

k
lic
Alternatively, the reaction may also occur in the following route.

C
oxidative) [Fe (CO) 1]+ 1- Substitution of

[Fe(CO)s] +1 2 )cis-[Fe(CO) 41 2J
addition ofI+ as 1- ( S 2) CO by 1-
(16e,OS = 0) 18e,OS = + (18e.OS = +2)
At the second step, substitution preferably occurs at the cis-position of the existing I-ligand (cf. Sec.
10.2.1). A similar situation is illustrated for [Os3(CO)3(PPh 3)2] reacting with 12.
• Sometimes, the five coordinate 18e complexes of tJ8 electronic configration may experience an
oxidative addition to give the six coordinate 18e complexes through the dissociation of one original
ligand due to the steric factors. It is illustrated for the trigonal bipyramidal complex,[Os(CO)3(L)2]'
L = PPh 3 reacting with 12, [Fe(CO)s] also reacts with 12 in the same way as discussed above.
L L L
OC
~O
I OC"" 1/ 1
OC"" 1/ 1
""I
Oxidative addition of 12 -CO +1 2 -co
and dissociation
of one CO: OC
/ I S •
oc
/0"
I CO
I- •
oc
/os
I
L L L
ry
(18e,0) (18e, +2) (18e, +2)
(intermediate)
ra
At the first step 1+ adds as 1- causing a 2e oxidation of the metal centre (i. e. the metal donates a
pair of electron to 1+). It gives the intermediate where another atom of 12 resides as 1- in the outer-sphere,
ib
i.e. the intermediate is a 1:llectrolyte. Then, nucleophlic substitution of a CO group by 1- occurs to
yl
give the final product (cf substitution at the cis- position of I; Sec. 10.2.1).
m
Oxidation of metal centre by two unit
he
X
Mn + + X_ Y~ Mn+2 /
'\y
lc
It is believed that the nonbonding electron pair on 'M' is first donated to the incoming X+ Lewis
ea
acid (i. e. R+ or H+) and then the lone pair on Y- is donated to the metal centre acting as the Lewis
acid. Both the fragments (i.e. X and Y) are more electronegative than the metal and thus it is
th
assumed that informing the M-X and M-Y bonds, the metal centreformally loses two electrons.
Thus the metal centre is formally oxidised by two units during the oxidative addition of X-Y to
e/
the metal centre through the X- Y bond cleavage.

t.m
Oxidative addition in the compounds of nonmetals

SnCl 2 + Cl 2 ----7 SnCI4 ; 2FeCl 2 + Cl 2 ----7 2FeC1 3 ;
PF3 + F 2 ----7 PFs; Me2S + 12 ----7 Me2S12
e
• Generally, the square planar tLS-complexes of Group 8, 9 and 10 experience the oxidative
er
addition. The heavier congeners in a particular group are the better candidates for the oxidative addition.
H
In a period, the earlier members are the better candidates to experience the oxidative addition.
k
w
o.~
lic
~Cti
Gr. 8 Gr. 9 Gr. 10 u:2
~
0-r-
C
w 0
x
"Ow
C
:~ c5 Fe(O) Co(l) Ni(lI) w_

C..c
!2~ Ru(O) Rh(l) Pd(lI) -;'w

Q) .... C u
a:~ 'wco·~ffi .Q
c
....: == 05(0) Ir(l) Pt(lI)
(.) Q) 4l111-------------- ~ ~~
Ux"O
Increasing tendency to experience Ewco
the oxidative addition
• The metal basicity (i.e. nucleophilicity) is well known for the metal complexes of the heavier
congeners, specially in the low oxidation states. This tendency increases in a group from top to bottom.
It is evidenced from the relative rates for the oxidative addition of CH 31 with [(lls-Cp)M(CO)(PPh 3 )]
(M = Co, Rh, lr).
(lj5-e0 lj5-Cp + lj5-Cp
I.
M·~
+ CH 3 0 •
1 CH 3-migralion,
---~.. /M~,f'
1 0
/ (oxidative addition) / I~
M
entry of I-as Ph pic
ry
OC PPh 3 Ph 3 P CH 3 a ligand. 3 I \
(18e, +1) CO
ra
(18e, +3) (18e, +3) CH 3
Relative rate: 1(CO): I.4(Rh): 8(lr).
ib
• B~sides the £is-systems, other systems like d10, d 6 , etc. can also experience the oxidative addition.
yl
[W(bpy)(CO)3] + SnCl 4 ~[W(bpy)(CO)3CI{SnCI3)]
(I6e,0) (I8e, +2)
m
2
he
[Pt (C 2H 4 )(PPh 3 )2] + Mel ~[Pt (11 -C 2H 4 )(CH 3 )(PPh 3 )2(1)]
2 4
-C H ) [Pt (CH 3 ) (PPh 3 )2(1)]
(I6e,0) (I8e, +2) (I6e, +2)
lO lc
Note: For the d systems (e.g. PtO, Pdo), the trigonal planar complex participates in oxidative addition.
• Oxidative addition leading to Ie oxidation of the metal centre is also known in the reaction of
ea
[CO(CN)5]3- with R-X (alkyl halide).
th
2[Co(CN)s]3- + R-X~[R-Co(CN)s]3- + [CO(CN)5 X]3-

7
(d ,I7e,+2) (d 6 ,I8e,+3) (d 6 ,I8e,+3)
e/
The above mentioned reaction is of tremendous importance in organic synthesis as [RCo(CN)s]3-

t.m
may be used for the synthesis of different organic compounds. It is illustrated in the following
example.
H+ + +
(NC)4CO -C==N - - - - 3.~ (NC) Co-C==NH ----.. (CN)4 CO - C ===NH
e
I ;, tV I
V ~ _
er
R R
OH
H
(Overall charges not shown)

R-C==N + Co(III)-Complex
k
The Ie-oxidative addition reaction rate occurring in [CO(CN)5]3- depends on the R-X bond strength.
lic
The reactivity order is: R-I ) R-Br ) R-Cl. The rate is first-order in both the cobalt complex and the
alkyl halide (R-X). The reaction has been explained in terms of atom transfer involving the free
C
radical intermediate.
[Co II (CN)5]3- + R - X~[COIII(CN)5X]3- + R.
[Co II (CN)5 ]3- + R. (fast) [R _ CO III (CN)5 ]3-

• [CO(CN)5]3- also experiences Ie oxidative addition in the reaction with H 2•
2[Co II (CN)5]3- + H 2 ~2[COIII(CN)5H]3-

But the above reaction leading to pentacyanidohydridocobaltate(lll) does not occur through the free
radical mechanism. It passes through a concerted process to be discussed later. The above reaction can
explain the catalytic property of [CO(CN)5]3- in homogeneous hydrogenation reactions (ef activation
of H 2, ef Sec. 10.12.11).
+H 2
PhCH=CH 2 ) PhCH 2CH 3·
[ Co(CN)s]3-
The hydrogenation reaction probably passes through the following routes.
ry
CH 2 =CHX
+[Co(CN)sHr-
(olefm
[
-. .Into ) ) (NC)sCo-CH 2CH 2X
..insertIOn
r-
J3- -----~)CH3CH2X
+[CO(CN)5 H
ra
the Co- H bond
ib
The first step indicates the insertion of olefin into the Co--H bond to give the cobalt-alkyl complex.
At the next step, the alkyl group is released as an alkane in the reaction with cobalt hydride.
yl
The reaction may also occur through the following free radical mechanism.
m
[Co(CN)sH]3- +CH2=CHX~[Co(CN)s]3-+CH 3CHX
he
l[CO(CNlsHt
lc CH 3CH 2X
ea
• Addition of dioxygen (0 2), olefins and BF3 to Vaska's complex - simple Lewis acid-
base adduct formation or substitution or oxidative addition? Oxidative addition without
th
the increase of coordination number and bond rupture of the molecule to be added.
e/
(a) O 2 addition: O 2 (dioxygen) binds with the Vaska's complex trans-[lr(CO)(PPh 3 )2(X)] without
the cleavage of the '0-0' bond (i.e. X-Y adds without the cleavage of X-Y bond). In the so called
t.m
oxidative addition reactions, the X-Y bond cleaves and the fragments as the anions (i.e. X-, Y-) bind
as the ligands. The dioxygen adduct can be represented in two ways.
Trigonal bipyramidal adduct:
e
PPh 3 PPh 3
O?""J/o
)Ir-ll
er
OC 0
l/i~~i
I
and
H
X I 0
PPh 3 PPh 3
k
lic
x-acceptor strength: C 2X 4 ) CO ) PPh 3 ) O 2 , Explain the positions of PPh 3 ligands in the tbp adducts.
C
Dioxygen adduct of Vaska's compound (see Sec. 9.13 and Vol. 3 for details)
If O 2 is passed through a benzene solution of Vaska's compound, the yellolv colour changes to
orange. This change is reversible and bubbling N2 gas can restore the original colour. It may be
noted that O2 also binds in a reversible fashion with hemoglobin and myoglobin.
[Ir(CO)CI (PPh 3 )zJ + 02 ~=={Ir(CO)O (11 2-0 2 ) (PPh 3 )2 ]
For X = Cl: 0-0 = 130 pm (cf 128 pm for O 2)

For X = 1: 0-0 = 151 pm (cf 149 pm for Oi-)
°
It is evident that in the chlorido complex, O 2 exists as 2- (i. e. superoxide) while in the iodido-
complex, O 2 exists as 01- (i.e. peroxide). Cl is more electronegative than I. Consequently, in the iodido-
complex, the electron movement from the metal to the n* of O 2 is more. Thus apparently, more electron
loss from the metal centre in the adduct of iodido-complex, leads to Ir(lll) from Ir(l) (i. e. 2e loss) while
in the chlorido-complex, the less electron loss leads to Ir(l) to Ir(ll) (i.e. Ie loss). Thus in this sense,
though the addition of O2 does not involve the complete rupture of0-0 bond, but there is an oxidation
ry
(by le to 2e) at the metal centre with the simultaneous weakening of the 0-0 bond. Thus the reaction
may be considered as an oxidative addition reaction.
ra
(b) Olefin addition: On the other hand, the said dioxygen adduct may be simply considered as a
simply Lewis acid-base adduct of Ir(I). In the adduct, dioxygen simply acts as a n-acid ligand. The
ib
similar situation arises for olefin addition. The olefins can act as the n-acid ligands and in the adduct,
yl
the 'C-C' bond length depends on the extent of n-electron donation from the metal centre into the
vacant n*-MO of olefin. However, the 'C-C' bond does not rupture and it may adopt the 'C-C'single
m
bond length at the limiting situation when the olefin (e.g. C 2(CN)4) acts as a powerfuln-acid ligand.
he
""'/
-C
Mn~ b
lc (Oxidative addition of olefin)
ea
7'"
Metal olefin Metallacyclopropane
th
(c) BF3 adduct of Vaska's complex: In the adduct, attainment of the higher oxidation state (i. e. + 1
to +3) of iridium is indicated by a substantial increase of the vco value (1967 cm- I to 2067 cm- I).
e/
Thus the BF3 addition as a Lewis acid to the complex may be argued as an oxidative addition.
t.m
(d) Oxidative addition without bond cleavage is also illustrated in the following example.
L~ / 0
/Pt
"cI + 2L, (L = PPh 3 )
e
L
er
/ "CF3
F3C
H
Interestingly, in the above reaction, there is no increase of coordination number (which generally
occurs) and to maintain it, there is an expulsion of two ligands.
k
lic
10.6.2 Scope of the Oxidative Addition Reaction

The C-H bond is generally unreactive because of two grounds: high bond energy (-470 kJ
C
mol-I) and low polarity. Oxidative addition ofC-H generates the M-C and M-H bonds. Formation
of these M-H and M-C bonds are the driving forces to break down the C-H bond. It is illustrated
below.
Ph2iQ!Ql
oxidative addition
(intramolecular
.. CI-- r&PPh 3
cyclometallation)
PPh 3
In fact, activation of the C-H bond in this way find many applications (cf see Secs. 10.8, 9).
Similarly, H-H (i.e. H 2) is highly unreactive (cf. bond energy -430 kJ mol-I) but it can be activated
through the oxidative addition leading to the metal-hydride bonds. The catalysing action of [Co(CN)S]3-
in the hydrogenation of olefins has been already illustrated. In fact, the same principle works for
hydrogenation of different unsaturated organic compounds (Lf Sec. 10.13.3).
ry
10.6.3 Stereochemistry of Oxidative Addition
The important observations are given below:
ra
(i) The nonpolar substances like H 2 adds in a cis-fashion.
ib
(ii) The alkyl halides (R-X) generally give the trans-addition product (i.e. the fragments R and X
are at the trans-positions in the product); but some cis-products may be obtained also.
yl
L
m
OC"",I/H
+ H2 Ir
he
----..
CI/I
L
""'H
lc (cis-product)
ea
Nine isomeric products possible
th
-------)
Y"
3 major isomers (L ligands in trans-positions)
e/
+ 6 minor isomers (L ligands in cis-positions)

t.m
Kinetically controlled the major 3 isomers (2 L ligands in trans-positions) can be identified by

considering the VIr-C1 values. VIr-C1 (CI trans- to CO) appears in the range 300-310 cm- I. Addi-
tion of MeCI gives V Ir-CI values 305 cm- l (CI trans- to CO) and 260 cm- l (CI trans- to Me).
Addition of Mel or MeBr gives the only V Ir-CI band at 300 cm- I (i.e. isomer i).
e
The structures of the possible 9 isomers can be drawn. Some examples are:
er
Me Me L
H
L"",I/CI L"",I/I L"",I/CI Ki netically controlled product

Ir Ir Ir The isomer (i) very often appears
OC/I"""L oc/I"'-,
k
OC/I""'L as the major product which is

kinetically controlled.
lic
I CI Me
(i) (ii) (iii)
C
(Me, I in trans-positions) (Me, I in cis-positions) (Me, I in cis-positions)

(2L in trans-positions) (2L in trans-positions) (2L in cis-positions)
V 1r- C1 :::::: 300 cm- 1 V1r-e1 :::::: 260 cm- 1 V1r-e1 :::::: 300 cm- 1
10.6.4 Mechanism of Oxidative Addition Reaction

(i) Concerted reaction pathway: If X-Y is nonpolar (e.g. O2, C1 2, Brb H 2) then the reaction
passes specially in nonpolar conditions through this pathway. In this one-step concerted
process, the new bonds are produced in the cis-positions. In general, it can be represented as
follows.
~::~ .--- ABMO
(M)d ~ ABMO(X-Y) i.e.
n..
~ {if
'. - ::~
. • . • . • .• +
.• .• .• .• .• ,.•.• •. •. •. •. .•
.•;;/,,,,, . '>+.'.
~~~{j
X
I----+M /X
Y
""v (cis-product)
ry
> ...
ra
For H 2, this pathway is well established where two hydrides remain in the cis-positions in the
ib
product. The concerted reaction generates a three centre transition state in which H 2 binds in a
112-fashion (presently, 112-H2 ligand is referred to as nonclassical binding fashion). Then the
yl
112-H2 complex (i.e. activated state) experiences the H - H bond breaking to give the dihydridido
m
complex.
he
L L
I ,f:i OC~I/H
L", /Co
rds
.. OC
(fast)
..
CI/
Ir
"'L + H2
CI
""
/ Ir' "
lc
I"" ~
:I • Ir
I
C I / ""'-H
L = PPh 3
ea
L
Vaska's complex L
In the nonclassical complex of dihydrogen (i.e. 112-ligand), the 112-H2 ligand actually acts as a
th
'It-acid ligand and receives electron from the metal centre into its vacant antibonding orbital. This
electron pushing into the cr*-MO of H 2 weakens the H-H bond and eventually it becomes H 22-leading
e/
to the complete rupture of H-H bond. It gives the dihydrido complex. The concerted mechanism
t.m
explains why the hydrides remain in the cis-positions of the final product.
Activation of hydrogen through hetersolysis (i.e. ionic mechanism)

In presence of a strong base like Et3N, heterolysis of H 2 occurs giving rise to H+ (abstracted by the
e
base) and H- that binds with a suitable metal centre.

er
[RuCI 2(PPh 3)2J + Et 3N + H 2~ Et 3N+HCI- + [RuCI(H) (PPh 3)2J

H
Dihydrogen vs. Dihydrido complex (see Sec. 9.12)

k
There are evidences that in some cases, there is an equilibrium between the dihydrogen
lic
(1l2-H 2 complex, i.e.. nonclassical complex) and dihydrido complexes.

C
H H H
M
n+ - I i.e., M
," I
I
I --.:::-.
-.:::--- M
nV
, I
H '. : "'H
H
( ) )
V V
Dihydrogen complex Dihydrido complex
(i. e. nonclassical complex) (i.e. classical complex)
The above equilibrium has been experimentally found in [W(CO)3(H 2 )(P -i-Pr3)2].
Here it is important to mention that the bond energy in H 2 is very high (ca. 450 kJ mol-I) but
oxidative addition leads to formation of two cis- M-H bonds which can compensate the required bond
dissociation energy. It illustrates the activation of H 2 and this is of tremendous importance in commer-
cial fields (e.g. hydrogenation of alkenes).
Here it is important to note that the isotope effect due to substitution of H by D is marginially
small. It indicates that in the activated complex, the H-H bond breaking is not much important. O 2
ry
and olefin addition in Vaska's complex also proceeds through the concerted mechanism.
O 2 and olefin addition in Vaska's complex also proceeds through the concerted mechanism.
ra
Ionic mechanism vs. concerted process
ib
trans-[I r(CO)CI(PPh 3)2]
yl
Vaska's complex
m
both cis- and trans- ~
HX I I ~
HX - - - - .
~ cis-addition
he
addition (polar media like (nonpolar media
DMF) like benzene)
lc
Hand CI will form two cis-bonds exclusively if the oxidative addition passes (in nonpolar
ea
media) through the concerted process. It happens so when the reaction is carried out in the
nonpolar media. In the polar media, HX (X = CI, Br) will be dissociated and an ionic mechanism
will operate to give both the cis- and trans-addition products.
th
HX~H(solvated)+ + X (solvated)-
e/
J
[ML 4 + H(solvated)+ ~ [ML 4 HT X(so)vatedf )[ML 4 (H)(X)]
t.m
The cationic ML4 H+ (C.N. 5) complex may undergo isomerisation through an intramolecular
path (ef Berry pseudonotation). Coordination by X- to this rearranged 5-coordinate species will
give the product that will have both the eis- and trans-addition products.
e
er
(ii) Nucleophilic attack by the metal on carbon of R-X: If X-Y (as in R-X) is polar, then it
can act as an electrophile. Then the metal centre as a nucleophile attacks the electrophile (i.e. C-centre
H
~ 6+('6-
"L R
I . L" I L
k
L
M~,," :
.. R-X 0+ (i-
M--- R----X
lic
[L4 M] ~ I
(16e)
L/ I"',~ &- L/IL
L
C
II
J L", I /L
R
.~
------:J . M
L/ I "'L
X
(18e, octahedral)
of alkyl halides) in an associative path (i.e. SN2). It produces a transition state having a considerable
amount of polarity. The transition state may produce a three membered cyclic transition state. This is
illustrated for ML4 (16e complex).
In general, the path can be outlined as follows:
[LnM(-GR1 R2R3)(X)]
ry
ra
ib
yl
Concerted and SN2 path
m
Both the pathways lead to the same rate law. In both the cases, the metal centre uses the nonbonding
he
electron pair (it is in the axial direction for the square planar complexes) for the nucleophilic attack
on the electrophile.
lc
The evidences to support the associative path (i.e. SN2) are given below.
ea
• The rate shows a first order dependence on each of the reactants, i.e. starting complex and
R-X (i.e. X-Y), i.e.
rate oc [ML4 ] [R-X].
th
• For the oxidative addition of alkyl halides (RX), the rate follows the following order.
R: tertiary alkyl) secondary) primary alkyl; X : I ) Br ) CI ) F. It indicates the effects of R-
e/
X bond strength and relative stability of R+ (to receive the nucleophilic attack in SN2 path) on the rate
t.m
process. This observed order, in fact, is in conformity with the both SN2 mechanism and free radical
mechanism (cf stability order of Re).
• The entropy of activation (~S:t) is highly negative. It supports the associative path. The activa-
tion parameters largely depend on the solvent polarity. It is also expected from the polar transition
e
state.
er
• The rate increases with the increase of nucleophilicity of the metal complexes. This is expected
from the proposed associative path where the metal centre makes the nucleophilic attack.
H
• The transition state (denoted by II) is a limiting case which resembles the transition state for the
nucleophilic substitution of alkyl halide (cf SN2 path for nucleophilic substitution of alkyl halides in
k
organic chemistry). Thus, it is reasonable for the observed inversion of configuration at the C-centre
lic
(where the metal makes the nucleophilic attack). This transition state also rationalises the predomi-
nant trans-addition product (i.e. X and Yare in trans positions). However, some cis-addition product
C
is also possible.
• Here it should be mentioned that the nucleophilic attack by the metal centre will occur in the
vacant antibonding orbital of X-Y. This will allow the rupture of the X-Y linkage.
(iii) Associative path for the 18e square planar complex: If the starting complex is a square planar
18e-compex, then to adopt the associative path, at first, one ligand is to be dissociated to give a
16e-complex, that experiences the above mentioned path. This is illustrated below.
-L ~x~
:::;;;::===~ [:ML 3 ] ~ [ML3X]+Y-
+L (16e) (SN 2 ) (16e)
As in [M(PPh 3)4] (M = Pd, Pt; d lO system), the active species is [M(PPh3)3].

[M(Ph 3)4] ~ [M(PPh 3)]3 + PPh 3
(18e) (16e)
~ (:.2- P:th)
ry
[M(PPh3)3R] +X (16e)
ra
(16e)
Similarly, if the starting five coordinate complex maintains the 18e count, then it can follow the SN 2
ib
path in two ways.
yl
-L +X - Y
[ML s] • [ML 4] --~.~ [ML 4Xry - -----il.~ [ML 4XY]
m
(18e, trigonal (16e, square (SN 2) (16e) (18e, octahedral)
bipyramid) planar)
he
I~ [MLsXrV -
+x _ V -L, +V -
• [ML4 XVj
(L neutral)
(SN 2)
(18e)
lc
(18e, octahedral)
ea
(iv) Free radical mechanism: This is outlined in Scheme 16.6.4.1.
Collapse
LnMX+ + x - V ~
th
LnMx+1(X), y.
L--.y-----J
e/
t.m
e
er
H
~ x-v
k
lic
L MX+2(Y) + x· ~ Chain
n 2 reaction
C
Scheme 10.6.4.1 Radical mechanism of oxidative addition.
The characteristic features of free radical mechanism are given below:

• The process proceeds through the successive Ie-transfer steps (cf. SN2 path involves 2e-transfer
at a single step). Such ale-transfer path has been mentioned for oxidative addition of R-X to
[Co(CN)s]3-(C! Sec. 10.6.1).
• The process can be initiated by the free radical generators like 02, organic peroxides, etc. The
free radical scavangers (e.g. hydroquinone) may prevent the process.
• The process first generates the cage complex which can directly collapse to give the product. In
other way, the radicals may diffuse to participate in the chain reactions.
Very often, both the free radical path and SN2 path go on simultaneouly. The rate law is the same
for the both pathways. In terms of the rate law, the three possible pathways-concerted path, SN2 path
and free radical path cannot be distinguished. However existence of free radical can be proved by
direct and indirect evidences.
• The inversion of configuration at 'C' experiencing the nucleophilic attack during the oxidative
addition of R*-X suggests the operation of SN 2-path.
ry
The radical mechanism is supported by the following observations:
ra
rate acceleration by the free radical generators (e. g. 02) and presence of light favouring the
generation of free radicals; rate retardation by free radical scavangers; loss of stereochemistry,
ib
i.e. recemisation of R*-X; free R· and X· may combine to produce R*-X and this leads to
racemisation.
yl
10.7 REDUCTIVE ELIMINATION
m
In general, the reverse of oxidative addition reaction is described as the reductive elimination reaction.
he
Such examples have been discussed in Sec. 10.6. In some cases, the molecule eliminated is different
from the one added oxidatively.
lc
The groups to be eliminated must be present at the adjacent cis-positions. This is why, it is
described as 1, 1- or geminal elimination.
ea
R
/ Reductive
th
LnM1n+2)+"" -e-Ii-mi-na-ti-on---il~· LnMn+ + R - R', (R, R' = organic group or H)
R'
e/
t.m
-----I~. Et -Me + LAuMe

e
or
Me-Me + LAuEt
er
H
-----i~. Me - Et + LAuMe
L = PPh 3
k
lic
~ Ph-Ph + PtL2
C
(Biphenyl)
The ease of reductive elimination of different organic groups as RH (i.e. alkane elimination) from
[PtH(PPh 3)2(R)] follows the sequence.
R: C6Hs)C2Hs)CH3)CH2CH=CH2
• In some cases, before the reductive elimination of the adjacent groups, other ligands may be lost.
Me
~I
-=--- Au--Et
+L
------il.~ Me - Et + LAuMe
Me
I
ry
• Sometimes, addition of ligands before the reductive elimination step may favour the reductive
ra
elimination. This may place the groups to be eliminated in a more favourable position.
It is illustrated in the following reaction.
ib
yl
m
he
Rate = {k1[H+] + k2 [H+] [CI-] }[complex]
To explain the experimental findings, it has been proposed that addition of H+ occurs at the first step
to cause an oxidative addition (i.e. H+ becomes H- in the complex). At the next step, reductive elimi-
nation of CH4 occurs.
lc
ea
+
L" / l 0 L HI CH l +
=;;
th
CH
3 H+,S ,,/ 3 (rds)
Pt ~ Pt ------.
e/
CI/ "L CI/I"L

as = +2) S
t.m
(16e, (16e, as = +2)

(18e, as = +4) (T.S.)
(k1-path) (S = Solvent like MeOH)

e
l
er
L" / l CH
0 L HI CH 0
H
3 H+,CI- " / 3 (rds)
CI/ "L
Pt ~
c,/I"L
Pt ------.
k
(16e, as = +2) CI
as = +2)
lic
(16e,
(18e, as = +4) (T.S.)
C
(~-path)
The above mechanism explains the rate law, i.e. k1-path involving the first-order dependence on
[H+] and k2-path showing the first-order dependence on both [H+] and [CI-].
Note: Formation of ylid from RsP is a classical example of reductive elimination.
Me
Me", I /H
P--C-H ~ Me 3P=CH 2 + CH 4
Me/I \H
Me
10.8 ACTIVATION OF C-H BONDSTHROUGHTHE OXIDATIVE ADDITION

The C-H bonds are very strong (cf alkyl-H ~ 430 kJ mol-I; Ph-H ~ 460 kJ mol-I). This is why
the C-H bonds are quite unreactive. Petroleum and natural gas are constituted by hydrocarbons.
Thus activation of the C-H bond is of tremendous importance in the chemistry of petroleum and
related industries. This activation may be attained through the oxidative addition of the R-H bond.
ry
R'
Oxidative / R" - X
LM-R' + R-H ~ LM-R • R-R" + LMR' + HX
ra
addition "
d I
ib
Metal + Hydrocarbon :nClionalisalion
complex derivatives f
yl
LM-R+R'-H
m
The metal complex to which oxidative addition of R-H occurs is regenerated after functionalising
the hydrocarbons. Thus the metal complex can act as a catalyst in the process of functionalising hydro-
he
carbons.
Oxidative addition of R-H (i.e. insertion of the metal centre into the R-H bond, i.e. the C-H
lc
bond) is thermodynamically favourable if the sum of M-C and M-H bond energies exceeds that
of the 'C-H' bond energy.
ea
10.8.1 Characteristic Requirements of the C-H Bond Activation
th
For the oxidative addition of R-H, the required complex must be in low oxidation state and coordinatively
unsaturated.
e/
Such complexes are generally produced in situ through the reductive elimination either by
photochemically or thermally. The examples are:
t.m
[(l1s-CsMes)Rh(PMe3)(R')(H)] (reductive~imination) {(l1s-CsMes)Rh(PMe3)] + R'-H

e
[( l1S-CsMes)M(PMe3)(H)2] hV,lowtemp.
(reductive elimination)
)[(
11 s_C S M e S )M(PMe 3 )] + H 2
er
S s
[(l1 -CsMes)M (PMe 3)]+ R - H (oxidative addition) { (l1 -CSMe S)M(PMe 3)(R)(H)]
H
'M = Rh, Ir'

The complex acting as a catalyst to experience the oxidative addition of R-H bears the
k
lls-pentamethylcyclopentadienylligand (i.e. lls-CsMes denoted as lls-Cp*) instead of the unsubstituted

lic
ligand lls-Cp. This choice arises so to avoid the possibility of the activation of the C-H bond of
Cp leading to an undesirable product. In fact, when [Ti(llS-Cp)2] was attempted to prepare, it led to
C
the dimeric product as shown below.
Dimeric product of [Ti("S-CP)2]

Titanocene => J,1-("s: "s-fulvalene)-di-J,1-dihydrido-bis(cyclopentadienyltitanium)
In fact, for the complexes bearing the 115-Cp ligand, the activated C-H bond may lead to some
unwanted product as in [Ti(115-Cp)2]. In *Cp, there is no C-H bond and consequently there is no
possibility of C-H bond cleavage to generate the untoward product. Moreover, Cp* is more
electron rich than Cp and consequently Cp*makes the stronger metal-ligand bond. The electron
pushing effect of the Me-groups makes the metal centre electron rich to favour the oxidative
addition. The bulky *Cp ligand hinders the unwanted associative reactions also.
ry
Mechanistic steps leading to functionalising the hydrocarbons through the activation of the
C-H bonds can be outlined as follows:
ra
ib
,.,H H
'"
,.
Oxidative addition
yl
"'c-
LMR' + - C - H ------~~~ (L)(R')M:, (L)(R')M/
,
/
/'"
m
"C-
/'"
he
lc
ea
Reductive R~-------:H
/ elimination
,,
,
(L)M-C- ,'
'" (L)'M~
th
+R'-H
C---
e/
/'"
t.m
The activation of the 'C-H' bond depends upon the ease of three centre two electron (3c - 2e) bond
formation producing the three membered cyclic transition state.
10.8.2 Examples of the C-H Bond Activation

e
er
/ PMe3
hv, -H 2
(a) [(1l5-*Cp)lr(PMe 3 )(H)2l + CSH12 ~ (1l5-*Cp)lr-- H
H
'"
(cyclohexane)
CS H11
k
~
lic
hv
C
(-H 2 )
i.e.
H
/r",
H PMe 3
Ir" "
PMe 3
/ PMe3
hv, -H 2
(b) [(1l5-*Cp)Rh(PMe 3 )(H)2l + C3 Ha ~ (1l5-*Cp)Rh - - H
'" C3 H7
hv
/co
(c) [(1l5-*Cp)lr(CO)2l + CH3C(Meh----"""'i.~
. (1l5-*Cp) Ir" H
(-eO) "
CH 2CMe 3
ry
(d)
ra
ib
yl
m
he
[(1l5-*Cp)Rh(PMe 3 )(PhHH)] [C 3 HaJ 7. *
K eq = [ ]
(1l5-*Cp)Rh(PMe 3 )(C 3 H7 )(H) [CsHsJ
=:: lc
2.5 x 10 , C
P
= C 5 Me 5
ea
The interesting observations of the above equilibrium mixture are:
(i) [(1l5-*Cp)Rh(PMe3)(Ph)(H)] is thermally more stable than [(1l5-*Cp)Rh(PMe3)(C3H7)(H)] be-
th
cause of the higher Rh-aryl bond strength compared to that of the Rh-alkyl bond.
(ii) [(1l5-*Cp)Rh(PMe3)(Ph)(H)] experiences the reductive elimination of C6H 6 at higher tempera-
e/
ture (ca. 60°C) while [(1l5-*Cp)Rh(PMe3)(C3H7)(H)] experiences the reductive elimination of

C3Hs at lower temperature (ca. -15°C) (cf Rh-aryl bond strength) Rh-alkyl bond strength).
t.m
(iii) The C-H bond in alkanes is weaker than in arenes. The higher stability of
[(1l5-*Cp)Rh(PMe3)(Ph)(H)] than than of [(1l5-*Cp)Rh(PMe3)(C3H7)(H)] indicates the
preference for activation of an arene.
e
(iv) The above reaction illustrates the functionalisation of hydrocarbons through the C-H bond
activation.
er
(e) Activation of methane:

H
k
lic
C
This reaction illustrates the activation of methane.

(t) Cyclometallation and orthometallation: It is well known that the coordinated triphenylphosphine
undergoes intramolecular cyclometallation through the C-H bond activation. This results from the
oxidative addition of the C-H bond. If the 'C-H' bond to be activated remains at the ortho-position
(with respect to the PPh 2-group, then such cyclo-metallation reaction is described as ortho-metallation).
CI"" /PPh 3 oxidative
/Ir" addition of
Ph 3 P PPh 3 C-H bond
ry
(16e, +1)
ra
(18e, +3)
(Addition of H+ as a H-ligand causes 2e-oxidation of Ir)
ib
yl
m
he
lc
ea
th
e/
In most of the examples, cyclometallation results from the activation of the C-H bonds of the
phenyl groups (present in the ligand PPh 3). However, there are also examples illustrating the activation
t.m
of the C-H bond of alkyl groups (present in PR3).

e
er
intramolecular
~
cyclometallation
H
k
lic
M-C bond formation through the intramolecular H-transfer is known in the reaction of [PdCI4]2-
C
with azobenzene. It gives the cyclopalladation (cf. Sec. 10.12.81) through the intramolecular C-H
bond activation.
(g) Agostic interaction vs. oxidative addition of C-H bond: It is now well established that
the 'C-H' bond can act as a ligand without the cleavage of the C-H bond. The M-H-C bond is
explained as the 3c-2e bond as in the B-H-B linkage. This ligating property of the C-H bond is
described as the agostic interaction (Greek word meaning to clasp or to draw towards). Agostic interaction
is now well documented in many complexes like [W(CO)3(PCY3)2] (Cy = cyclohexyl) where one
C-H bond of the cyclohexyl group interacts with W; [Ti(Me2PCH2CH2PMe2)CI3(Me)] where
T}2-CH3 coordination arises from the agostic interaction of the C-H bond of the Me-group.
ry
ra
Agostic interaction of the C-H bond
ib
Agostic interaction needs a vacant coordination site at the metal centre and generally donation of the
electron pair of the C-H bond leads to electron count 18, i.e. the bonding electron pair in the 3c-2e
yl
M-H-C bridge is considered for electron count.
Agostic interaction also activates the 'C-H' bond. It is believed that the limiting situation of the
m
agostic interaction leads to an oxidative addition of the C-H bond. In fact, the trinuclear complex
he
having the composition [Os3(CH3)(CO)1O(H)l exists in an equilibrium mixture of two forms - in one
form involving the agostic interaction and the other form involving the oxidative addition.
lc
ea
th
e/
(Agostic interaction) (Oxidative addition)

t.m
It is suggested that the agostic interaction of the C-H bond to the metal centre represents the
transition state for the oxidative addition of the C-H bond.
10.9 C-H BOND ACTIVATION THROUGH THE SIGMA-BOND METATHESIS
e
C-H bond activation through the a-bond metathesis has been argued for some £to-complexes where
er
oxidative addition cannot occur. The higher oxidation state disfavours the oxidative addition of the
C-H bond. This has been found for the lanthanide organometallic compounds. It is illustrated for
H
activation of CH4.
[(1l5-*Cp)2M-CH3l + l3CH4 ~ [(1l5-*Cp)2M-l3CH3l + CH4, (M = Lu, V).
k
Here l3CH4 exchanges l3C with the CH 3 group attached to M. If the reaction is carried out in
lic
deuterated cyclohexane, there is no indication of activation of the C-D bond (i.e. absence of exchange
between H and D). Probably, the bulky ligand *Cp does not allow the bulky hydrocarbon cyclohexane
C
to enter into the coordination sphere of the metal centre. Here it may be mentioned that the C-H bond
of the solvent is very often more reactive than the C-H bond of CH4. It may complicate the situation.
However, in the present case, the bulky *Cp ligands prevent the activation of cyclohexane (which is also
a bulky hydrocarbon).
9
H3 1:i - - - - - -H
I I
--.. : : ---. M- 13CH 3 + CH 4
I I
M- - - - - - - CH 3
a
(cf. a-elimination process, Sec. 10.5.2)
The proposed mechanism involves the formation of a four-centred transition state ending to
a-H hydrogen transfer.
In general it can be represented as follows:
R'-------H
I
I
R'-H
I
M-R' +R-H ~ I
I
~ +
I
ry
I
I
I
I
M-R
M------- R
ra
Such mechanisms to activate the 'C-H' bond occurs when the route through the oxidative addition
of the C-H bond is disfa voured. If the metal centre is in high oxidation state, then oxidative addition
ib
is very much unlikely.
yl
Decomposition of permethyls like [WMe6], [TaMes] is also believed to occur through a such
mechanism.
m
[WM] explosive
e 6 -d-ec-o....;;...m-po-sl-·ti-on~) [
W( = CH )3] + 3CH 4
2
he
M- - - - - - - - -CH 2
M---CH 2
I 1 _
I
I
I
I
I
I
I
lc
~ M===CH 2 + CH 4
ea
I I
CH 3 H I I
H3C---------H
th
10.10 REDISTRIBUTION (i.e. SCRAMBLING) REACTIONS

e/
Important types of the reaction are:

t.m
Scrambling of a group within a molecule:

(i) Scrambling of the bridging and terminal CO ligands in [(l1s-Cp)2Fe2(CO)4] (this will be discussed
in detail in Sec. 10.11).
(ii) Scrambling of bridging and terminal Me-groups in dimeric trimethylaluminum, i.e. A12Me6.
e
,,/,,/
er
Me Me* Me
AI AI
H
i.e. / "Me
' . / " Me
Me
k
Interchange of ligands between two different or same complexes.

lic
[Ni(CO)4]+[ Ni(*cotl=~[Ni(CO)x(*CO)y] (x+y=4)

C
[Ni (CO)4] + [ Ni (PF3 )4 ] ~ [Ni (CO) x (PF3 )y ] (x+y=4)

[SnCI 4 J + [SnMe4J~ [SnClx(Me)y ] (x+y=4)
For such reactions, the number and type of metal-ligand bonds do not change and consequently dH
is expected to be close to zero. In fact, such reactions enjoy the entropic favour, i.e. entropy of mixing
is positive. The exchange reaction is an entropy driven reaction.
Mechanistic paths for scrambling of Me-groups in A12Me6: This reaction has been studied
extensively. In terms of the PMR signal, it shows the fluxional property. At room temperature, it shows
a single PMR signal for all the Me-groups when Al 2Me6 is studied in tolune, but at low temperature,
the signal tends to split into two. In fact, at -65°C, it shows two distinct signals (2: 1 intensity ratio) for
the Me-groups (higher field/or the terminal Me-group and lower field/or the bridging Me-groups). The
possible mechanistic pathways for the exchange of terminal and bridging Me-groups are given below.
ry
Terminal
Me - protons
Bridging Me protons (r ~ 10.50)
ra
(r = 9.92)
ib
yl
m
he
-45°C (Peak broadening)
lc
ea
-30°C (Peak merging)
th
e/
(Sharp peak)
t.m
------------------------p~ H
(Magnetic field)
e
er
Fig. 10.10.1 Qualitative representation of the PMR spectrum of Al2Me6 at different temperatures.
H
Pathway I: Me ", Me* ,,; Me Me Me Me*

" AI><, ><AI /
,~, ~ AI(Me)i Me *) + AI(Me)3 ~ ""'/"'./
k
/AI" /AI"
/ )( )<, "
Me , " Me " , Me Me Me Me
lic
Here the rate determining step involves the dissociation of the dimers to monomers followed by
C
rapid recombination of monomers to dimers. This recombination may occur in different orientations.
Here one of the AI-Me-AI bridges undergoes rupture (i.e. one AI-Me bridge bond experiences
the rupture) at the rate determining step followed by the rotation about the remaining AI-C bridge
bond and reformation of the dimer.
The experimental evidences are in favour of the first pathway (i.e. dimer to monomer followed by
combination of the monomers). The activation energy (dE*) (::::: 65 kJ mol-I) remains more or less the
same for both the scrambling of Me-groups in Al2Me6 and the Me-exchange reactions between Al 2Me6
and InMe3 or GaMe3' i.e.
scrambling of Me-groups in A12Me6' dE* ::::: 65 kJ mol-I
ry
Al 2Me 6 +M(Me)2Me* ~AI(Me)5(Me*) + MMe 3.
ra
(M = Ga, In) dE* ~ 65 kJ mol-I
ib
It indicates that for the above two reactions, the rate determining step is the same. The Me-group
exchange reactions can be explained as followed:
yl
Al 2Me 6 ~2AIMe3 (rds)
m
AIMe 3 + M(Me)2(Me*)~AIMe2(Me*) + MMe 3)
he
Fast
AIMe 3 +AI(Me)2(Me*)~AI2Me5(Me*)
lc
ea
10.11 PATHWAYS LEADING TO STEREOCHEMICAL NONRIGIDITY AND FLUXIONAL
ISOMERISM IN THE ORGANOMETALLIC COMPOUNDS
th
10.11.1 Characteristic Features of the Stereochemically Nonrigid and Fluxional

Molecules
e/
These aspects have been discussed in detail in Sec. 10.9 of Vol. 2 and Chapter 12 of the present volume.
t.m
Here these are discussed in short.

For most of the molecules, one particular stereochemical arrangement is much more stable than the
other possible stereochemical arrangements. Such molecules are characterised by the large HOMO-
e
LUMO gaps. For some molecules, two or more stereochemical arrangements are possible because of
their comparable stabilities. Such molecules are stereochemically nonrigid. If such stereochemically
er
nonrigid molecules possess two or more chemically equivalent configurations, then such molecules
H
are referred to as the fluxional molecules.

Thus it can be stated as follows: all fluxional molecules are stereochemically nonrigid but all
k
stereochemically nonrigid molecules are not fluxional.

lic
For the fluxional behaviour, stereochemically nonrigid molecules produce the chemically indistin-
guishable configurations, and consequently the net energy change for the process in zero, i.e. dao =
C
dHo = L\So = 0, as there is no chemical change in this process. Thus the chemically indistinguishable
configurations differ only in the interchange of indistinguishable nuclei. It may be mentioned that if the
stereochemically nonrigid molecules produce the configurations which are not chemically equivalent
(e.g. cis- trans isomerism, polytopal rearrangement, etc.) then for such an interchange process, dCO is
not zero.
The above statement can be illustrated as follows: the four coordinate Ni(II)-complex, [NiX 2(PR 3)2]
(X- = halide) is stereochemically nonrigid and it remains very often in a dynamic equilibrium, tetra-
hedral ~ square planar (an example of polytopal rearrangement) and position of the equilibrium
depends on the temperature (see Secs. 2.3, 8.26).
Br
I
Ni
Br~ /PEtPh 2
Br/ I'PEtPh 2
~
Ph 2EtP
/Ni~
Br
, kinterconversion'" 1.6 X 105 S-1 at 25°C
PEtPh 2
ry
Tetrahedral, green, Square planars, red,
paramagnetic (S = 1) diamagnetic (S = 0)
ra
Thus the isomers of [NiX2(PR3)2] are not chemically equivalent and this is why though it represents
ib
the case of stereochemical nonrigidity but not the case of fluxionality.
It has been already mentioned (Sec. 2.11.7) that [Ni(CN)s]2- can have the both structures - square
yl
pyramid and trigonal bipyramid and both the structures even can exist in the same crystal of
m
[Cr(en)3] [Ni(CN)s], 1.5 H 20 (cf if the cation is replaced by [Cr(1,3-propanediamine)3]3+ then in the
crystal, only the square pyramidal anion, [Ni(CN)s]3- exists). It may be noted that the trigonal bipyramidal
he
[Ni(CN)s]3- is chemically different from the square pyramidal [Ni(CN)s ]3-. Thus this stereochemical
nonrigidity is not the example offluxionality.
lc
In fact, the polytopal isomerism does not illustrate the fluxionality. The common examples of
polytopal isomers remaining in equilibrium are:
ea
square planar (D4h ) ~ tetrahedral (Td); trigonal bipyramid (D 3h ) ~ square pyramidal (C 4v ); do-
decahedron ~ cube or square antiprism. (Note: Very often all types of stereochemical nonrigidity
th
studied by NMR studies are loosely described as fluxionality.)

e/
• Conformations of the molecules and time scale of observation: Time scale of different experi-
mental techniques to identify the stereochemical configurations of the molecules is of much importance
t.m
to describe the stereochemical nonrigidity. For example, ir (infrared) and Raman stectra of [Fe(CO)s]
indicate two types of CO groups (two axial CO groups and three equatorial CO groups in the trigonal
bipyramidal structure of [Fe(CO)s)] but 13C·NMR studies cannot distinguish the axial and equato-
rial CO groups, i.e. all five CO groups appear identical.
e
Each experimental technique observes a molecule on a time scale which is the characteristic feature
er
of the technique used. The time scale (i.e. required time to make an observation) is related with the
H
frequency of the electromagnetic radiation used as follows (cf Sec. 10.9.3, Vol. 2):
MM '" l!.- (i.e. Uncertainty Principle)

k
21t
lic
h 1
or, h (/).v) /).t ~ - ; or, ~t ~ ( )
C
21t 21t ~v
Taking /).V ~ v, we can write: /).t = 1/(2nv) i.e. time scale is inversely proportional to the frequency
of the exciting radiation used in the experimental technique. The ultraviolet, visible, infrared-Ra-
man spectra techniques are the relatively faster techniques (time scale ~ 10- 13 s) than the NMR tech-
nique (time scale ~ 10-s - 10-2 s).
If the energy barrier (i.e. activation energy) for the stereochemical changes is not high, then they can
change their configurations rapidly by using the thermal energies available at ordinary temperature. If
the time required for this interconversion of the stereochemical configurations is smaller than the
time scale of the experimental technique, then the technique cannot distinguish the stereochemical
configurations and such molecules are referred to as the stereochemical nonrigid molecules with
respect to that experimental technique. Thus a particular molecule nlay be considered stereochemically
rigid with respect to a particular technique but the same molecule may be describbed as the
stereochelnically nonrigid with respect to another technique whose time scale is relatively larger. It has
been conventionally accepted that stereochemical nonrigidity is studied with respect to the time
scale of NMR spectroscopy, i.e. stereochemical nonrigidity is studied by NMR spectroscopy.
ry
Now let us come back to the problem of [Fe(CO)s]. The infrared and Raman spectra are such faster
ra
techniques to record instantaneously the snapshot to the structural features of the molecule, i. e.
[Fe(CO)s] in the present case. Within the time scale of these faster spectral techniques, the interchange
ib
between the axial and equatorial groups of [Fe(CO)s] cannot occur and consequently two different
types of CO groups are identified. On the other hand, the NMR technique is a much slower technique
yl
and it actually records the time average structure of the molecule like [Fe(CO)s]. In [Fe(CO)s], the
m
mutual interchange between the axial and equatorial CO groups occurs much faster than the time scale
of NMR technique. This is why, the 13C-NMR technique cannot distinguish between the axial and
he
equatorial CO groups present in [Fe(CO)s].
• Study of stereochemical nonrigidity by NMR technique (time scale := 10-2 to 10-s s): It has
lc
been pointed out that the studies on stereochemical nonrigidity are carried out by NMR spectroscopy.
The rate of interconversion among the possible stereochemical configurations depends on the activa-
ea
tion energies and temperature [cf Arrhenius equation, k = A ex p ( _E:;t J]. It can be shown that if the
kBT
th
activation energies lie in the range 25-100 kJ mol- I then the rate constants for the said interconversions
fall in the range 102 - lOs S-I in the span of temperature -150 0 to + 150°C. To follow the different stereo-
e/
chemical arrangements of the stereochemically nonrigid molecules, NMR spectra are to be recorded
t.m
over a suitable temperature range.

• Characteristic change in the NMR signal with the exchange rate of NMR active nuclei
residing in different environments (cf. Sec. 12.2.15): The different nuclei (NMR active) in different
e
chemical environments (i.e. magnetically nonequivalent nuclei) give the different NMR signals. With
the increase of the exchange rate among these magnetically nonequivalent nuclei, the NMR signals
er
start to broaden and eventually they undergo merging or coalescence at a certain exchange rate and
no peak is noted. If the exchange rate increases further, then a sharp peak (i.e. one signal) corresponding
H
to the mole-fraction weighted average resonance of the different types of nuclei is observed. Thus for
the fluxional molecules, different NMR signals undergo peak broadening, merging (i.e. coalescence)
k
followed by a sharp single peak (weighted average resonance) with the increase of temperature.
lic
10.11.2 Stereochemical Nonrigidity in the Compounds of Main Group Elements and

C
Classical Coordination Complexes

(a) Inversion of pyramidal molecules: In ammonia, the inversion rate is extemely high (ca. 2.5 x 10 10
S-I). The energy barrier for the inversion is very small (ca. 25 - 30 kJ mol-I) and the process mainly
occurs through the quantum mechanical tunneling process. It may be noted that inversion ofNH 3 can
also occur through the symmetric bending (UNU) vibration, i.e. v2(A I) normal mode of vibration (cf
Fig. 12.1.8.1). By varying the bulkiness of the groups in the substituted amines (i.e. NR IR 2R 3), substi-
tuted phosphines (i.e. PR IR 2R3) and substituted arsines (i.e. AsR IR 2R3), the energy barrier for inversion
may be raised sufficiently (> 100 kJ mol-I) so that they can be resolved. For this inversion process, a
planar transition state is attained.
ry
(cf. Fig. 12.1.8.1)
ra
ib
(Pyramidal) (Planar) (Pyramidal)
yl
m
y .•
"
,,"
"
X
'"
:7
I
I
".
I
Y~A\:
, .
"
, ,,"I:
)<
I
lc
I
he A
/
X
"
I
··
.
:
'
",
.y
,,"
"
" I
·
ea
,
,
,
I
I
I
"
'\:
. I
I"
"
,
z Z
Z
th
(Pyramidal) (Planar) (Pyramidal)

e/
(b) General representation of inversion of pyramidal molecule AXYZ (A = central element)
Fig. 10.11.2.1 Process of inversion for the pyramidal molecules.

t.m
~
r Single doublet
U
(--25 C)0
e
er
----- I I ---------
~!
H
~ J p _F
k
(No resonance)
lic
JF-F~·
~ ~ '\ (Peak broadening)
r
C
A double A doublet
doublets triplets
~ (For 1 Feq )
(For 2 FaJ
(Berry's pseudorotation
I
0
(-_-_1_4_5_C_)_---, I causing the stereochemical
I I I I nonrigidity).
~Jp_F ~Jp_F.q
Magnetic field
Fig. 10.11.2.2 Qualitative representation of the 19F-NMR spectra ofPCl 2F3 at different temperatures I = for 31p and 19F. t
(b) Tetrahedral-square planar interconversion: [NiX 2(PR 3)2] can experience the stereochemical
change, tetrahedral ~ square planar with the activation energies in the range 45 - 50 kJ mol- 1 having
the interconversion rate constant about 10s S-1 at room temperature. It represents the case of
stereochemical nonrigidity but not the case of fluxionality because the two isomeric forms are not
chemically equivalent.
(c) Trigonal bipyramidal species: Berry pseudorotation or turnstile rotation can lead to the inter-
ry
change between the axial and equatorial groups to extablish the fluxional behaviour. The fluxional
behaviour of PFs, PCI 2F 3, CIF 3, PRxFy (x + Y = 5), etc. has been discussed in detail in Sec. 10.9 of Vol. 2
ra
and Sec. 12.2 of this present volume.
Note: (i) At very low temperature (say, -145°C) where the interconversion rate between the axial
ib
(Fax) and equatorial (Feq ) atoms through the Berry's pseudorotation is sufficiently slow (with respect to
yl
the NMR time scale), 19F-NMR spectroscopy can detect separately both the Fax and Feq . Further splitting
by the coupling of 31P, Fax and F eq can also occur.
m
Fax: doublet by 31p (i.e. 2 x 1 x I + 1= 2 x 1x 1+ 1 = 2) ; further splitting by Feq (I = ~) giving rise to
he
p
a doublet of doublets.
F eq : doublet by 31p; further splitting by two axial F-atoms producing two triplets
lc
(i.e. 2 x 2 x I Fox + 1 = 2 x 2 x 1+ 1 = 3) i.e. a doublet of triplets.
ea
(ii) At higher temperature, with the increase of interconversion rate between the Fax and F eq atoms,
the peaks start to broaden (say at -130°C) followed by disappearance of the resonance (say at
th
-110°C); then the appearance of a sharp doublet (say, at -25°C) indicating the F-atoms equivalent (i.e.
e/
interconversion rate between the Fax and Feq atoms is faster than the NMR time scale).
5-coordinate silicon compounds may also show the fluxional behaviour in the same mechanistic
t.m
pathway.
(d) XeF6: Stereochemical nonrigidity of this interesting molecule has been separately discussed in
the Sec. 10.9 of Vol. 2.
(e) Classical coordination complexes of coordination number six: Generally, octahedral com-
e
plexes are stereochemically rigid and consequently the fluxional behaviour, i.e. rapid tautomeric
er
rearrangements, is generally absent in the octahedral complexes. For this fluxional rearrangement in
the octahedral complexes, it needs generally the metal-ligand bond rupture and this is why, the rapid
H
tautomeric rearrangements do not occur. However there are some exceptions.

• = Fe, Au
k
td:~t3
lic
C
RP~P
H
(trans-)
(cis-)
Fig. 10.11.2.3 Interconversion between the cis- and trans- isomers of [M(H)iPR3)4] (M = Fe, Ru) through distortion.
(i) Generally, interconversion between the cis- and trans- isomers of [MX4Y2] type complexes
occurs through the metal-ligand bond dissociation followed by recombination (see Chapter 5). How-
ever, in some rare cases, this interconversion may occur through the intramolecular rearrangemrnt (i.e.
distortion of the complex). Such complexes are [M(H)2(PR3)4] (M = Ru, Fe).
At low temperature (ca. -50°C), two separate PMR signals appear for the cis and trans- isomers but
at relatively higher temperature (ca. +60°C), the signals collapse into a single multiplet indicating the
ry
rapid interconversion of the two isomeric structures (i.e., cis- and trans- isomers). This rapid
interconversion occurs through a nondissociative path and it is supported by the preservation of
ra
31p_1H coupling in the entire range of NMR study.
ib
(ii) The intramolecular rearrangement of [M(X-X)2Y2] and [M(X-X)3] can occur through the
twisting mechanism (i.e. Ray-Dutt twist and Bailer twist). This twisting mechanism has been discussed
yl
in detail in Chapter 5. This twisting mechanism leading to the stereochemical nonrigidity is favoured
m
(i.e. low activation energy which is thermally accessible) only under certain conditions. The trigonal
twist (i.e. Bailer twist) is facile and rapid only when the bite distance of the chelating ligand in
he
[M(X - X)3] is small, i.e. small twist angle. In such cases, the complex even in ground state configuration
is sufficiently distorted towards the trigonal prismatic configuration which represents the required
lc
transition state of the process. Thus, it can attain the transition state at the cost of a little activation
F<,~C-NE~)
ea
energy that may be obtained from the thermal energy. The tris-chelate, bearing
th
3
small bite distance represents the case where Bailer twist can occur easily. Obviously, if the complex
possesses a regular octahedral geometry at the ground state then the activation energy for the Bailer
e/
twist process is fairly high (cf Chapter 5).

t.m
(f) Coordination compounds having coordination number greater than six: For the octahedral
complexes, stereochemical nonrigidity is the exception but for the complexes with coordination number
7 or higher, the stereochemical nonrigidity is the common phenomenon and stereochemical rigidity is
the exception. Here it may be noted that the 5-coordinate complexes also show the stereochemical
e
nonrigidity very often.

er
In fact, coordination compounds with coordination number higher than 6 show the facile polytopal
H
rearrangement. In such cases, the structures having the different possible stereochemical arrange-
ments differ marginally in energy (ca. a few kilojoules only) and the energy barrier for their
interconversion is also small. It makes them stereochemically nonrigid.
k
lic
ReF?, IF? are stereochemically nonrigid. An 8-coordinate complex of dodecahedral structure is

stereochemically nonrigid. In a dodecahedral structure, all the 8 ligands are not equivalent and they are
of two types. A slight distortion can produce either a cubic or square antiprismatic intermediate from
C
which two dodecahedral structures can be obtained with an equal probability. These two dodecahedral
structures represent the interchange of the two types of ligands (cf Fig. 2.11.10.3, Chapter 2). These
aspects have been discussed in detail in Chapter 2. Thus it is evident that for the interchange of two
types of ligands in trigonal bipyramid, square pyramid is the transition state or short-lived intermediate
and similarly for the interchange between the two sets of ligands in a dodecahedron, the square
antiprismatic or cubic intermediate is the required transition state.
trigonal bipyramid (I) ~ square pyramid ~ trigonal bipyramid (II)
dodecahedron (I) ~ cube or square antiprism ~ dodecahedron (II).
10.11.3 Fluxional Behaviour in Organometallic Compounds

In organometallic chemistry, fluxional behaviour is manifested well. Different types of stereochemical
nonrigidity is known.
(i) Internal rotation of cyclic polyenes: It is illustrated for ferrocene, i.e. [Fe(1l5-Cp)2] where at
room temperature, the two Cp-rings rotate rapidly to each other. It leads to the stereochemical nonrigidity.
ry
The rapid rotation of the pi-bonded Cp-ring (i.e. 115-Cp) makes the five protons equivalent in PMR
studies at all temperatures.
ra
(ii) Rotation of the coordinated olefin around the metal·olefin bond as in [(Tl 5·Cp)Rh(Tl 2.C 2H 4)2]:
There are two types of olefinic protons, i.e. Hi (inner proton) and H O (outer proton). At very low
ib
temperature (ca. -20°C) where the olefin rotation is sufficiently slow (with respect to the NMR time
scale), there are two PMR signals (1: 1 intensity) (Ho: an downfield multiplet; Hi: an upfield multiplet).
yl
But at the higher temperature where the olefin rotation is so fast that the NMR technique fails to
m
distinguish the outer and inner protons and only one PMR signal appears. Activation energy for this
rotation process is estimated as 63 kJ mol-I.
he
lc
ea
th
e/
t.m
e
er
H
k
lic
Fig. 10.11.3.1 (a) Internal rotation in ferrocene. (b) Rotation of the coordinated olefins around the metal-ligand bond
and qualitative representation of PMR spectra of of the ethylenic protons of [(1l5-Cp)Rh(lf-C2H)2l at different tempera-
C
tures.
Note: The PMR signal for the 5-equivalent protons of the 115-Cp ring is not shown in Fig. 10.11.3.1 b.
Here two, the outer protons are magnetically nearly equivalent. Similarly, the inner protons are nearly
equivalent. Thus, in terms of the ethylenic protons, the system is represented by AA'XX' (not by A 2X 2;
cf. Sec. 12.2).
(iii) Rearrangement of a-bonded cyclic polyenes: When a conjugated cyclic polyene is attached
to a metal centre through a a-bond, the metal-carbon a-bonding may hop around the ring. This type of
fluxionality is called ring whizzing by considering the apparent motion of the ring relative to the metal
centre. This is illustrated in the following examples bearing the lll-Cp linkage:
54
~CHH3)3
I I 2
3
---=-.
--=:---
4
3
8
1 1
H3
2
)3
----==-.
--=:---
365
2
Ge(CH 3 )3
1
---=-
~-
ry
(llS-Cp)Fe(CO)2 (llS-Cp)Fe(CO)2 (llS-Cp)Fe(CO)2
ra
56: 6 ~365
ib
---=-
~41 11 --=:---
yl
3 3 2 2 1
m
• For [(115-Cp)(111-Cp)Fe(CO)2]: In PMR spectra, two sharp lines are obtained at room tempera-
ture. It is expected that it should give:
he
One single line for 115-Cp, 3 signals (intensity ratio 1:2:2) for 1l1_Cp where there are three types of
protons: at the site M-C a-bond, two protons at the adjacent C-centres from the M-C bond; two
protons at the remaining two C-centres. lc
ea
M H'
th
(3 types of protons in the ratio 1:2:2)

e/
H'" H'"
t.m
III
Fig. 10.11.3.2 Three types of protons (i.e. H', 2H" and 2H with respect to the M-C a-bond in nl-Cp. The olefinic
)
protons, i.e. H", H", Hili and Hili are expected to give the downfield multiplet and an upfield multiplet for H'. Their
relative intensities should be 4: 1.
e
At room temperature, a single sharp line for IH or 13c_ NMR spectra of 1l1_Cp indicates that there
er
must a be a low energy barrier pathway for the rapid rearrangement to make all the protons magneti-
cally equivalent. AI very low temperature, it is reasonable to expect that IH-NMR for 1l1_Cp should
sdh
H
M~H
-- sq~
1 M 1
k
S 2 1,2-shift 1,2-shift 2
lic
\ ../ --"/
\\ /1 co: 2 H co:
M
C
4 3 4 3 4 3
5CfM
1,3-shift__
H
Scheme 10.11.3.1 Schematic representation of 1, 2-metal shift and 1, 3-metal shift for M(nl-Cp).
give three signals for three different types of protons. Similarly, the single sharp line for 1l1_Cp of
[(CH3)3Ge(Tl1-Cp)] predicts the same thing. The dissociative mechanism for the said rapid rearrange-
ment process does not find any experimental support. The possible intramolecular pathway for proton
averaging are: 1, 2-metal shift or 1, 3-metal shift.
In the hopping process outlined in Scheme 10.11.3.1, it appears that there is a motion of the ring
relative to the metal centre and this is why, it is commonly called ring whizzing. Experimental evidences
ry
indicate the 1, 2-shift rather than the 1, 3-shift. In the 1, 2-metal shift, at the transition state, the protons
H', and H" are more affected than the H"'-protons (cf Fig. 10.11.3.2). This is observed in
ra
IH-NMR spectra of the complex at very low temperature.
1, 2-shift vs. 1, 5-shift: For 1l1_Cp i.e. 1l1_CsHs system, 1, 2-shift and 1, 5-shift are identical and these
ib
cannot be distinguished from the NMR-studies. But in 1l1_C 7H7 system, the 1, 5-shift is physically
yl
different from the 1, 2-shift. It has been noted that in [Ph 3Sn(1l1-C 7H 7)], fluxionality (i.e. ring whizzing)
arises from the 1, 5-shift not from the 1, 2-shift.
m
• [Hg(Tl 1-Cp)2] vs. [Hg(Tl 5-Cp)2]: In [Hg(1l1_Cp)2], divalent mercury is covalently bonded (i.e.
a-bonded) to two Cp groups with two classical 'Hg-C' single bonds. In [Hg(lls-Cp)2], Hg 2+ is believed
he
to be bound ionically with the two Cp- rings as in [Mg(lls-Cp)2]. The IH-NMR spectrum of the Hg(II)-
compound gives one sharp line at room temperature and this is maintained even upto -70°C. It can be
lc
~
2
ea
H
\ I ,
\ I,
3 types
th
\H~ 2+
'.fI Hg of protons
6
(1 : 2 : 2).
e/
t.m
(ionic) (covalent)
[Hg(T) S-Gp)2] [Hg(T) 1-GP)2]
i. e. pentahapto complex i.e. monohapto complex

e
er
Fig. 10.11.3.3(a) Two possible structures of bis(cyclopentadienyl)mercury(II).

H
-X
H T)1_Cp protons tT)5_C P (protons)
H (T = 4.25) I"
(T = 5.6)
k
(-+ 30° C)
{
lic
H H
C
Fe Two signals for

./ ~(--100°C) H", H" and H''', H'" protonJts/ T)5_Cp (protons)
OC H' CO ~ ¥ (-r=5.6)
=3.7 f\ 1\.: = 4.0 n.. . H' p~oton of
.-Ie
T
"H H"
./ V ' -/1 /1
Tj-CP
(-r = 6.5)~
'''H H'"
Fig. 10.11.3.3(b) Fluxional behaviour (i. e. qualitative PMR specta at different temperatures) of
[(Tls-Cp)Fe(CO)iTl1-Cp)] (tetrahedral structure).
simply explained by considering the [Hg(115-Cp)2] structure. But its ir-spectrum cannot be explained by
considering this structure where the Cp-ring are symmetrically placed.
In the [Hg(111-Cp)2] structure, there are three types of protons in the ratio 1:2:2 and it should give
three PMR signals. Here it should be mentioned that the ir-spectrum (a faster technique for observation)
records the snapshots while the' NMR-spectrum (a slower technique for observation) records time
averaged structure. In fact, the ir-data rule out the [Hg(115-Cp)2] structure and to explain the NMR-
ry
spectrum, it is suggested that the ring whizzing is so fast even at -70°C that the NMR technique cannot
distinguish the three different types of protons in [Hg(111-Cp)2]. It is due to the very low activation
ra
energy for the said ring whizzing process.
• [(Tl 5·Cp)Fe(CO)2(Tl 1.Cp)]: The PMR signal for the 1t-bonded Cp ring (i.e. 115-Cp) gives a single
ib
sharp peak at t' = 5.6 at all temperatures (range +30°C to -100°C) due to the rapid rotation (cf Fig.
yl
10.11.3.1) of the ring to make all the five protons of the 115-Cp ring equivalent. For the a-bonded Cp
ring (i.e. ll1-Cp), there are three types of protons (1 :2:2) and three PMR signals are recored for these
m
ll1-Cp protons at very low temperature (ca. -100°C) when the ring whizzing process is sufficiently
slow. These three PMR signals arise at 't values -3.7, -4.0 and -6.5 with the relative intensities 2:2: 1.
he
The upfield signal ('t = 6.5) is due to the H' proton. But at higher temperature (ca. +30°C), the ring
whizzing process becomes sufficently fast (with respect to the NMR time scale) to make all the three
lc
types of protons of the ll1-Cp ring equivalent and a sharp single peak ('t ::::: 4.25) corrsponding to the
mole-fraction weighted average resonance of the three types of the protons is noticed (Fig. 10.11.3.3(b».
ea
Here it is worth mentioning that in the temperature range (+30°C to -100°C), no interconversion
between the 115-Cp and ll1-Cp ring is noted (cf [Ti(Tl 5 ·Cp)2(Tl 1·Cp)2] where the rapid interconversion
th
between the a- and 1t- bonded Cp-rings is noted; Fig. 10.11.3.8).

(iv) Rearrangement of the partially 1t·bonded cyclic polyenes: When a conjugated cyclic polyene
e/
is attached to a metal centre by some (not all) of its C-centres then also the metal-ligand bond may hop
around the ring (i.e. ring whizzing). These are illustrated in Fig. 10.11.3.4.
t.m
J--~4
M
O
6
~ 5
e 20Ms ~
e
2 6 6
1
H/ \=======.7-- ~4
er
2 3 ~5
3 3
4 4
(1l1-coordination)
H
(1l3-coordination) (1l4-coordination) (1l6-coordination)
y -----~)
\
(Cyclopentadienyl) (Cycloheptadienyl)
k
(Cyclooctatetraene i.e., COT)

lic
(a) Some representative conjugated cyclic polyolefins bound to the metal centre not by all C-atoms
p76
C
~ 15
1 4
2 3
RU(CO)3
RU(CO)3
(b) Ring-Whizzing leading to fluxionality in [Ru(114-CgHg)(CO)3]
Fig. 10.11.3.4 Ring-Whizzing leading to fluxionality in the complexes having the partially 1t-bonded cyclic polyenes.
In such cases, ring whizzing may occur by 1, 2-shift and/or 1, 3-shift. The examples showing such
fluxionality are:
[(11 4-C xH x)Ru(CO)3], [(11 6 -C xHg)Cr(CO)3], (CgH g is cyclooctatetraene, i.e. COT)
The phenomenon is illustrated by taking the example of [(11 4-C gH g)Ru(CO)4]. Its IH-NMR spectrum
(Fig. IO.II.3.5b) at room temperature shows a single sharp line. The same thing happens for the
13C-NMR spectrum. This observation can be simply illustrated by considering the l1 S-C sHg (i.e.
ry
llx-COT) where all the protons (or carbons) are equivalent. But the X-ray diffraction studies proves the
11 4 -COT not ll x-COT. When the IH-NMR spectra of the complex were recorded at very low temperature
ra
(ca. -150 a C) then four signals for four different types of protons (Fig. 1O.II.3.5a) were noted. It is
ib
due to the fact that at very low temperature, the ring whizzing is quite slow compared to the NMR time
scale and NMR can detect the four different types of protons. But at room temperature, the ring
yl
whizzing process is much faster than the NMR time scale and then IH-NMR spectrum gives the time
m
averaged signal.
(v) Allyl rearrangement through the Tl 3 - 11 1 - Tl 3 process: The 113-allyl complexes (e.g.
he
[(1l3-CH 2C(Me)CH 2)PdCl(PPh 3 )]) are the representative examples of fluxional molecules. In a 113-allyl
moiety, there are three types of hydrogens in the ratio 1:2: 2. With respect to the middle hydrogen (H m ),
lc
there are two hydrogen atoms (He) occupying the syn or cis positions and two hydrogen atoms (H)
occupying the anti or trans-positions (cf Fig. IO.II.3.6a).
ea
th
e/
t.m
e
er
H
k
lic
C
RU(CO)3
(b) Qualitative representations of the 1H-NMR spectral patterns
(a) 4 types of hydrogen in [(1l4-C aHa)Ru(CO)3l
for [(1l4-C aHa)Ru(COhl at different temperatures
Fig. 10.11.3.5 Structure and PMR spectra (at different temperatures) of [(1l4-C g Hg )Ru(COh].
The 'H-NMR spectrum of a typicall113-allyl complex at low temperature show three signals for
three types of protons. The separate signals due to terminal hydrogens (i.e. He' H t ) are split into doublets
by the nontenninal, i.e. middle H-atom (H m) while the signal due to H m is split by four terminal H-
atoms. Thus, the signal due to H m appears as a multiplet. But, at a relatively higher temperature, the two
doublets for the two types of tenninal H-atoms, i.e. He and H t tend to collapse into a single doublet, i.e.
at a higher temperature, it shows only two types of protons-four equivalent terminal proton and one
middle or nonterminal proton. The presence of four equivalent tenninal protons indicates the rapid
intramolecular rearrangement between the cis- and trans-protons, i.e. He ~ Ht within the NMR
ry
time scale. It is suggested that the rapid scrambling of the terminal cis- and trans- protons occur
through the 11 3 -11 1-11 3 process (Fig. 10.11.3.6). 113-Allyl changes into 111-allyl i.e. allyl group becomes
ra
a-bonded to the metal through one of its tenninal carbons, then rotation about the C-C single bond
and reformation of the 113-allyl complex lead to cis, trans-proton equilibriation.
ib
yl
Hm
I M
H~ ~C"I/Ht
m
C C --
/ '\
he
Ht He
113-allyl YJ1-allyl
(a) Three different types of
protons in 113-allyl system
lc
(b) Fluxional behaviour in trihapto (1l3}-allyl organometallic complex
ea
th
e/
t.m
(i)
(relatively higher
temperature)
e
er
H
(ii)
k
(very low temperature)

lic
C
(c) Qualitative 1H-NMR spectra of fluxional 113-allyl system. (i) One multiplet (5 components, splitting by 4 equivalent
terminal hydrogens, i.e. 2H e + 2H t ) for Hm ; one doublet (due to splitting by Hm ) for time averaging four terminal hydrogens
(2H e + 2H t ). (ii) two large doublets (splitting by Hm) for 2H e and 2H t terminal H-atoms-indicating three different types of
protons (i.e., Hm , 2H e and 2H t )·
Fig. 10.11.3.6 Structure and PMR spectral behaviour of 113- a ll y l system.
(vi) Rearrangement of 1t-bonded allene: In the adduct ~ ,f tetramethylallene and [Fe(CO)4]' there
are three types of protons in the ratio 1: 1:2 in the st::l( i~ ~u ucture. These protons are: three in cis-
position and three in trans-position with respect to the [Fe(CO)4] moiety and six in a plane
perpendicular to the carbon-iron bond. In fact, at low temperature (ca. -60°C), the PMR spectrum
of the complex indicates three signals for these three different types of protons. But, as the temperature
increases, the spectrum collapses to a single signal representing the time average environment of the
twelve protons, i.e. at higher temperature, the rapid equilibriation among these protons makes them
equivalent with respect to the NMR time scale. The pathway for this rapid equilibriation probably
involves the migration or hopping of the [Fe(CO)4] moiety around the allene 7t-system.
ry
ra
ib
yl
m
he
Fig. 10.11.3.7 Fluxional behaviour in the adduct of tetramethylallene and irontetracarbonyl.
lc
(vii) Exchange of mode of binding, e.g. (J-7t exchange: In [Ti (11 1- C P)2(11 5-Cp)2]' there are two
ea
types of Cp-rings. But at a relatively higher temperature (ca. 62°C), IH-NMR spectrum of the complex
shows only a single peak indicating the equivalence of the 4 Cp-rings (Fig. 1O.11.3.8a). Thus at this
th
temperature, the mutual interconversion among these ligands occurs so fast that NMR technique cannot
distinguish their different chemical environments. At low temperature (ca. -27°C), this dynamic process
e/
leading to the mutal interconversion between the 11 1 and 11 5 modes of binding of the Cp-ring the
t.m
e
er
H
k
lic
C
------.~ H
(a) Qualitative PMR-spectra of [Ti(1l1-Cph(1l5-Cp)2] at different temperatures. The two signals observed for 115-Cp and
111-Cp at low temperature (e.g. - 27°C) broaden and collapse into a single one at higher temperature (e.g. 62°C). The
spectrum (at - -80° C) identifying the 3 different types of protons of 111-Cp is not shown here.
ry
ra
(b) Change of the mode of binding of the Cp-rings in [Ti(111-Cp)2(T}S-Cp)2]'
ib
Fig. 10.11.3.8 Structure and qualitative PMR spectra (at different temperatures) of [Ti(T}1-Cph(T}s-Cp)2l.
yl
becomes sufficiently slow and then the NMR technique can identify the different chemical environments
of protons present in the 111-Cp and 115-Cp rings. This is why, with the decrease of temperature, the
m
single lH-NMR peak tends to split into two peaks of equal intensity. Here it may be mentioned that
he
though in 115-Cp, all the protons are equivalent in Tll-Cp, there are three types of protons (cf. Fig.
10.11.3.2). But at this temperature (i.e. -27°C), the IH-NMR technique cannot distinguish these three
types of protons (number ratio 1:2:2) present in 111-Cp. Thus at -27°C, the mutual interconversion rate
lc
between the 111-Cp and 115-Cp rings is sufficiently slow with respect to the time scale of NMR, but the
ea
dynamic process (i. e. ring whizzing) leading to the mutual interchange among the three types of
protons present in the 111-Cp ring is too fast to be detected by NMR. If the temperature is lowered
further to about -80°C, then the dynamic process leading to the mutual interconversion among the three
th
types of protons of 111-Cp becomes sufficiently slow to be detected by NMR. Thus at -80°C, lH-NMR
technique can detect the protons (which are equivalent) of Tl 5-Cp, and three different types of
e/
protons (in the ratio 1:2:2) of Tll-Cp.

t.m
The dynamic process leading to mutual interconversion among the three types of protons present in
111-Cp is called ring whizzing and it occurs through the 1, 2-metal shift. This process has been dis-
cussed already (cf. Scheme 10.11.3.1). The dynamic process leading to the exchange between the
111-CP and 115-Cp ligands in [Ti(111-Cp)2(1l5-Cp)2] is shown in Fig. 10.lI.3.8b.
e
For [SC(CP)3]' the IH-NMR spectrum at relatively higher temperature (say ~ 30°), shows only a
er
single peak, i.e. all the Cp-rings are equivalent in terms of NMR. But at lower temperature (ca. -30°C),
the IH-NMR spectrum of the compound indicates that there are two types of protons in the ratio 2: 1.
H
It supports the structure [Sc(Tl l _Cp)(Tl 5-Cp)2] where the cr -1t exchange leading to the mutual exchange
between the 115-Cp and 111-Cp rings is too fast at 30°C to be detected by NMR, but this dynamic process
k
is slowed down sufficiently at -30°C so that the IH-NMR technique can detect the 115-Cp and
lic
111-Cp rings. But, even at -30°C, the dynamic process leading to the mutual exchange among the three
types of protons in 111-Cp is too fast to be detected by NMR. To identify the three different types protons
C
present in the 111-Cp ring by 1H-NMR, the temperature is to be lowered further.

Note: In [(Tl 5-Cp)Fe(CO)2(Tl l -Cp)] (cf. Fig. IO.11.3.3(b», no indication for the interconversion
between the 11 5- and 111-Cp rings was noted in the temperature range, +30°C to -100°C.
(vii) Scrambling of the bridging and terminal carbonyls: The carbonyl scrambling leading to the
fluxional behaviour is a very much common phenomenon in di- and polynuclear metal carbonyls. This
carbonyl scrambling arises from the fact that in a typical dinuclear system, for the different possible
modes of binding of CO to the metal centres, the energy does not change « 30 kJ mol-I) remarkably.
The two limiting situations of these different possible modes of binding are the terminal CO-ligands
and symmetrical bridging CO-ligands (cf. Fig. 10.11.3.9).
,8, ,
O~\
I:
M--M~
..
.. ,__
I:
1,"
M, , ,
,, ,
",
I~M'~
,,
"'-CO
ry
",
, ,,'
'C
ra
(1 ) o
(3)
ib
Fig. 10.11.3.9 Concerted process of carbonyl scrambling in a typical dinuclear system. 1 and I' =:> terminal-CO groups;
yl
2 ==> symmetrical bridging-CO groups; 3 and 3' => transition state for the CO-exchange process; energy difference
between the terminal (1, 1') and bridging (2) systems is marginally small; the transition state (3, 3') is of relatively higher
m
energy (ca. by 30 kJ mol-I).
he
Energetically, the systems bearing the bridging and the terminal CO groups are very much compa-
rable and the transition state for carbonyl scrambling process needs the small activation energy (ca.
30 kJ mol-I) which is very small.
lc
ea
Bridged VB. Nonbridged Structure (cf. Sec. 9.4.4)
th
o
(~O
"
e/
-~ .. :1
~ M---M
t.m
M M
:1 ..
""'/
c
II
ocJ
o
e
er
(Bridged-Nonbridged tautomerism)
The difference in stabilities between the bridged and nonbridged structure largely depends on
H
the size of the metal ions. The larger metal atoms prefer the nonbridged structure because the
longer M-M distance will strain the bridged structure. This is why, in a particular group, the
k
heavier congeners prefer to adopt the nonbridged structure. For example,

lic
[M 3(CO)12]: M = Fe (two bridging CO); M = Ru, Os (no bridging CO)

C
[M 4(CO)12]: M = Co, Rh (three bridging CO); M = Ir (no bridging CO).

In a period, because of the same ground, the late members (relatively smaller in size) prefer the
bridged structure. For example, [Mn2CO)1O] adopts the structure [(OC)sMn-Mn(CO)s] without
any bridging CO while [C0 2(CO)8] exists as an equilibrium mixture of both the bridged and
nonbridged structure.
• [(115.Cp)2Fe2(CO)4]: The classical example to illustrate the carbonyl scrambling is

[(lls-Cp)2Fe2(CO)4] which can exist in cis- and trans forms in solution (Fig. 10.11.3.10). From the
solution, the cis- and trans-isomers can be isolated.
ry
ra
ib
yl
(cis-) (trans-)
m
Fig. 10.11.3.10 Equilibrium mixture of cis- and trans forms of [(1l5-CphFe2(CO)4]
he
, . . . . - - - - - [(1l5.Cp)2 Fe2(CO)J - - - - - - ,
Crystallisation Cooling a warm
under a reduced
pressure
lc solution under a
nitrogen atmosphere
ea
cis-form trans-form
th
That the both cis- and transforms remain in a dynamic equilibrium in solution are supported by
infrared (ir) (see Fig. 9.4.11.4) and NMR spectroscopy. Simultaneous existence of the cis- and trans-
e/
isomers indicate that there are two types of Cp-rings (two 115-Cp rings in the cis- isomer are equivalent
but these are different from the two equivalent 115-Cp rings present in the trans- isomer) in the equilib-
t.m
rium mixture. In fact, IH-NMR spectrum of the system at very low temperature (ca. -70°C) gives two
signals, but with the increase of temperature, these two peaks tend to collapse and ultimately at +28°C,
e
er
H
k
lic
C
Fig. 10.11.3.11 Qualitative representation of the PMR spectral patterns of [(1l5-CphFe2(CO)4] at different temperatures.
At low temperature (e.g. -70°C) two signals for two different types of Cp-rings in the equilibrium mixture of cis- and
trans- isomers.
they merge into a single peak. Obviously, at -70°C, the cis- trans- isomerisation process is sufficiently
slow so that NMR technique can distinguish the cis- and trans- isomers (in other words, two different
environments of the Cp-rings). But, at +28°C, the process is so fast that the NMR technique cannot
distinguish the two isomers and rather it represents their time averaged structure.
The 13C-NMR spectrum of the system indicates that the cis- trans interconversion process is
accompained with the scrambling of the terminal and bridging CO groups. Thus 13C-NMR
ry
spectroscopy proves:
rate of cis ~ trans isomerisation = rate of carbonyl scrambling
ra
The simple rotation around the Fe-Fe bond without the opening of the bridging of co groups
ib
cannot occur because of the central rigid ring system. Even if it occurs, then it can explain the
cis ~ trans isomerisation but not the carbonyl scrambling. .
yl
The pathway for the two processes occurring simultaneously at the same rate is illustrated in Fig.
10.11.3.12.
m
The proposed mechanism involves the simultaneous opening of the two CO-bridges leading to a
nonbridged dinuclear species [(Tl5-Cp)(CO)2Fe - Fe(CO)2(Tl 5-Cp)] followed by the bridge reforma-
he
tion giving rise to the cis-trans isomerisation and CO scrambling simultaneously. Here it may be
mentioned that in the nonbridged dinuclear intermediate, rotation around the Fe-Fe is not prevented
lc
and this rotation is quite likely to occur before the bridge reformation. In fact, this rotation is respon-
ea
sible for the cis-trans isomerisation. In the bridge reformation step, from the nonbridged dinuclear
species any CO-group can swing to the bridging position. It leads to CO scrambling.
Figure 10.11.3.12 illustrates the same transition state (or short-lived intermediate) which is the
th
nonbridged dinuclear species, [(1l5-Cp)(CO)2Fe-Fe(CO)2(1l5-Cp)] for both the cis ~ trans isomeri-
e/
sation and CO-scarmbling process. This is why, the rates for these two processes are the same.
o o
t.m
II II
*C *CO C *CO
*CO *CO
/"" I
(Cp)Fe--Fe(Cp)
I ~
1/""1
e
(CP)Fj" /ie(CP) (CP)Fe"", /Fe(Cp)

I I
er
co "c co co co C
* II II
o
H
o
(Nonbridged dinuclear species)
k
O~
lic
o
oc""'- /8~ /CP CP"",- /8~ /Cp
C
Fe Fe Fe Fe
C/ ~/
~
'co OC/ ~ / ""'-CO
p
~
o o
(trans) (cis)
(Cp = l1S-CsHs)
Fig. 10.11.3.12 Carbonyl scrambling and cis ~ trans isomerisation in [(1l5-Cp)2Fe2(CO)4].
(Note: It may be noted that scrambling of Me-groups in Al2Me6 occurs through the formation of AIMe3
mcnomer.)
• [(Tl5-Cp)2M02(CO)6]: The fluxional behaviour (i.e. carbonyl scrambling) in terms of the

13C-NMR spectroscopy of [(Tl5·Cp)2M02(CO)6] can be explained in the same way (Fig. 10.11.3.13).
ry
ra
ib
Fig. 10.11.3.13 Fluxionality (carbonyl scrambling) in [(1l5-CphMo 2(CO)6]'
• [Rh4(CO)4]: In [Rh4(CO)12], the Rh-atoms are placed at the four vertices of a tetrahedron and out
yl
of the 12 CO groups, there are three bridging CO groups. The fluxionality (i.e. rapid scrambling of
m
these all CO groups), in terms of 13C-NMR spectroscopy, of the molecule leads to the rapid movement
of the 12 CO groups over the entire tetrahedral skeleton. It occurs in a series of steps and in each step,
he
three bridging CO groups open up in a concerted process to give a nonbridged intermediate. (i.e. 12 CO
groups remain as the terminal groups; each Rh-centre possesses three terminal CO groups; Fig.
10.11.3.14). Bridge reformations from this nonbridged intermediate also occur in a concerted process.
lc
At this step, all the terminal CO groups are equally probable to swing as the 3 bridging CO groups
ea
and all the Rh-Rh bonds are equally probable to insert the CO-bridges. This process leads to the
rapid scrambling of all the CO groups over the entire tetrahedral skeleton.
th
e/
t.m
e
er
H
k
Fig. 10.11.3.14 Scrambling of 12 CO groups over the entire tetrahedral skeleton in [Rh 4 (CO)12] (i.e. M = Rh).
lic
C
~
p p
Fig. 10.1.3.15 Trigonal bipyramidal structure of [Fe(COh(P-P)].

Conclusion: In di- and polynuclear carbonyls, the bridged and nonbridged structures differ slightly
in energy. Thus the energy required for the formation of the intermediate for the scrambling process is
very small.
(ix) Berry pseudorotation and 5-coordinate carbonyls: It has been already mentioned that the 5-
coordinate compounds (both of main group elements and transition elements) are very much
stereochemically nonrigid. Fluxional behaviour of [Fe(CO)s] has been already disscussed. It has been
ry
already stated that ir-spectra can distinguish the axial and equatorial CO groups but 13C-NMR cannot
distinguish them at a relatively higher temperature. The fluxional behaviour of the compound (cf Fig.
ra
10.11.3.15) closely related with [Fe(CO)s] is quite interesting.
ib
The 13C-NMR spectrum of the compound gives a I:2: I triplet (i.e. all the CO groups are magnetically
equivalent). Anyone of the CO group can act as a pivot group for Berry-pseudorotation and consequently
yl
all the three CO groups become equivalent through this rapid dynamic process (i.e. a rapid intra-
molecular averaging process).
m
Now coupling between two equivalent 31p nuclei (I = 1/2) and three equivalent CO groups can explain
he
the I:2: I triplet. Here it may be mentioned that the much faster experimental technique like infrared
spectroscopy can detect the three nonequivalent CO groups.
10.12 REACTIVITY OFTHE COORDINATED LIGANDS

lc
ea
10.12.1 Principles behind the Activation of Coordinated Ligands: Factors Favouring the
Nucleophilic and Electrophilic Attack on the Coordinated Ligands
th
The properties of a free ligand are very much different from those of the coordinated ligands. The
properties of a coordinated ligand depend on the nature of the metal centre and nature of the other
e/
ligands remaining coordinated with the metal centre. In fact, in the coordinated ligands, the electronic
t.m
environment differs singnificantly from the electronic environment of the free ligand. This electronic
environment which controls the reactivity depend on the three basic metal-ligand bonding interactions.
• ligand to metal a-bonding (i.e. a-basicity of the ligand)
e
• ligand to metaln-bonding (i.e. n-donor property of the ligand)

er
• metal to ligand n-bonding (i. e. n-acidity of the ligand)

The net effect of these three metal-ligand bonding interactions determines the resultant electronic
H
environment (i. e. electron density) of the coordinated ligand.

The electronic environment of a ligand changes due to its coordination with a metal centre. Due to
k
polarisation in the coordinated ligand, it may have different reactivities towards the nucleophile or
lic
electrophile depending on the condition (i.e. net electronic effect). These nucleophilic and electrophilic
attacks on the coordinated ligand will be discussed in detail. The electronic effect may also change the
C
acid-base property of the coordinated ligand.

A. Acid-Base property of coordinated ligand: If the metal centre in the complex acts basically as
an electron withdrawing agent, then the coordinated ligand becomes a poorer base, i.e. stronger acid.
M-NH 3 ~[M-NH2J- +H+, M-OH 2 ~[M-OH]- +H+
;H 2 0(pK u ""lS.74).[Fe(OH 2)6J+ (pK u ""2.7)
Coordinated NH) or H 20 can show the protonic character, if the metal centre is sufficiently electron
withdrawing (e.g. COllI, Felli, Hg II , etc.).
V
N~N-H
+
(pyrazinium)
ry
ra
~ l2+
ib
l3+
(H3N)5RU-N~N+-H ~ (H3N)5RU-N~N + H+, pKa > 0.6
yl
m
Protonated pyrazinium acts as a stroger acid when present in the complex of Ru(lll) and acts as a
weaker acid when present in the complex of Ru(ll) compared to the free protonated pyrazinium. In fact,
he
Ru(III) basically withdraws the electron cloud but the lower valent Ru(II) can act also as a better
'It-donor (i.e. Ru(ll) ~ 'It *-MO of the ligand) to increase the electron density in the coordinated ligand.
lc
B. Stereochemical change in a coordinated ligand: Sometimes, for the requirement of coordina-
tion, a ligand may have different conformations in its complexed state. For example, free bpy exists
ea
mainly in the transoid form but coordinated bpy adopts the cisoid form for chelation. Here the transoid
and cisoid forms arise with respect to the C-C single bond and these are denoted as s-transoid and
th
s-cisoid ('s' denoting the single bond with respect to which orientation of the ligand is considered). It
arises so for the s-transoid and s-cisoid forms of butadiene.
e/
t.m
e
(s-cisoid)
er
C. Nucleophilic attack on the coordinated ligands (cf Secs. 10.12. 6 and 8) : If in the nletal-ligand
interaction, electron cloud is pushed (net effect) to the metal-centre then the ligand becomes electron
H
deficient. It happens so when the a-basicity and 'It-basicity of the ligand are more predominant than the
'It-acidity of the ligand. Obviously, this situation is favoured when the metal centre is in high oxidation
k
state and the metal centre possesses the vacant d-orbital to receive the electron cloud from the ligand
lic
through the rc-bond, and when the other ligands remaining coordinated with the metal centre are
electron withdrawing. Obviously, these are the typical properties of the hard metal centres and their
C
Lewis acid properties are the main controlling factors. Such typical metal ions are: Mn 2+, Fe 2+, Fe 3+,
C0 2+, C0 3+, Ni 2+, Cu 2+, Zn 2+, etc. There are so many representative examples of activated nucleophilic
attack on the coordinated ligand.
Nucleophilic attack in terms of FMOs (cf. Fig. 10.3.1)

In terms of frontier molecular orbitals (FMOs) of the reactants, HOMO of the nucleophile
interacts with the LUMO of the electrophile (which experiences the nucleophilic attack) (cf Fig.
10.3.1). Complexation with a metal centre may affect the energies of the HOMO and LUMO of
the ligand supposed to get the nucleophilic attack.
(i) Nucleophilic attack on the coordinated CO: Obviously, this situation arises when
d(M) ~ n*(CO) n-bonding is relatively less important as in the case of carbonyls of heavier congeners
and early members.
~
n ~ ////0
ry
8- 8+ 8- 8+
M+ :C~O:~M-C==O~M===C===O:> M-C
~ :Nu - ~ :Nu -
ra
"'-NU
ib
Nu- = H-, A-, OH-, etc.
yl
Attack by H-, R- and OH- gives the formyl complex, acyl complex and hydroxycarbonyl complex
m
respectively (see Sec. lO.12.8E for details).
(ii) Hydrolytic cleavage of the coordinated ligand: The representative examples are the hydrolysis
he
of esters, amides, peptides and phosphates. Coordination by the carbonyl oxygen or phosphate oxygen
with the metal centre polarises the 'C-O' or 'P-O' bond. Then the nucleophile can favourably attack
lc
the C or P centre. The nucleophile may be H20 or OH-. In biological system, the metal hydroxide,
alkoxide or the functional groups like -OH, -C0 2, etc. present with the protein chain can act as the
ea
nucleophiles.
th
I 8+
NH
C 8-
e/
o .. M
IC
NU~ c-o
8+ 8-
----.M ----l.~. Product;
~
~
t.m
A-C -Nu .. Product

I
CHR
'"'OR
(Hydrolysis of ester)
I (Hydrolysis of peptide linkage)
e
er
H
k
lic
(Hydrolysis of monophosphate ester)

C
M(~~ ~ M(~~ + ROH, (Nu- = HPl
O=+~
-------:1. .
oAo
Nu-
(Hydrolysis of coordinated amino acid ester)

ry
Hydrolysis of coordinated nitrile; hydrolytic product amide remains coordinated
Nitrile (RCN) coordinated in [Ru(NH 3)5(NCR)]3+ hydrolyses about 106 times faster than that in
ra
[Ru(NH 3)s(NCR)]2+. It is reasonable as Ru(III) is more electron withdrawing than Ru(ll) to polarise the
coordinated ligand R-C:=N. .
ib
yl
iNU-(=H,o)
m
he
M~ / C - O H
c~
M
N
N lc H
ea
(Nucleophilic attack on the 2-cyano group of the coordinated 2-cyano-phen ligand)
th
~
EtOH
M-N (Nu-= EtOH)
e/
~-NU
t.m
elll
N
OEt
e
(Alcoholysis of the 2-cyano group of the coordinated 2-cyanopy ligand)

er
R
H
I R
(-N= ~=N-)
#C~ I
k
.. (H N)5CO '_1I-N~ "'N

III N;r'\
(NH)
35C0 -
"--/N
====C-R _
~IIN+jJ
/C--='N
lic
3 (= Nu-)
3
,~ (H 3 N)5CO -
III
N
"~N
I
C
I
_N
tetrazolate ligand
Nucleophilic attack by azide on the coordinated nitrile
Note: The hydrolase activity of the metalloenzymes (e.g. peptidase, phosphatase, etc.) depends on the
ease of the nucleophilic attack on the coordinated ligand (see the anthor's book, Bioinorganic Chemistry).
Sometimes, metal coordination neutralises the charge (as in the case of phosphate ester) and it favours
the approach of the nucleophile and the charge neutralisation also gives an entropic benefit through
the desolvation of the reactants.
Decarboxylation of f3-keto acid: It occurs in the following path illustrated for decarboxyla-
tion of acetone dicarboxylic acid.
o ~o
~CY
0, 90~ (~
1 (11
ry
M
~--H~p--~~.CH--C--CH--COH +M
ra
3 II 2 2
ib
The electron withdrawing inductive effect towards the metal centre which acts as a Lewis acid
yl
favours the decarboxylation process. Greater electron withdrawing inductive effect will obviously
favour the process better. In fact, [Cu(bpy)]2+ can catalyse the process better than [Cu(aq)]2+. The
m
1t-acidic property of bpy makes the metal centre more electron deficient and it pulls the electron
flow better in the desired direction.
he
(iii) Nucleophilic substitution on the benzene ring (cf Sec. 10.12.8): Benzene ring is electron rich
lc
and its chemistry is dominated by the electrophilic substitution reactions (e.g. Friedel-Crafts reac-
tion, alkylation). But if an electron withdrawing moiety like M(CO)3 (M = Cr, Mo W) can be attached
ea
with the benzene ring then the benzene ring becomes electron deficient to experience the nucleophilic
attack. In fact, benzene being 1t-bonded with Cr(CO)3 group experiences the nucleophilic substitution
th
easily. Thus, benzene can befunctionalised and then the M(CO)3 group may be removed easily by using
the mild oxidising agent like ]2.
e/
[ Cr(r(C6H6)J~[(T\6_C6H6)Cr(CO)3J
t.m
[ Cr(T\6-C6H6 )2] + [Cr(CO)6J~2[(T\6_C6H6)Cr(CO)3 ]

e
x
l-
er
~4_C6H6)
X
H
(11 6 ) + R-
or (x= H, CI)
(planar)
k
Cr-R
lic
(l1S-coordination)
/Cr
I "CO Cr /1\
OC /1"
OC OC CO CO
C
CO CO CO
(18e, OS = 0)
(18e; OS = 0) (18e, OS = 0)
fast ~ -x-
~
Cr(lII) + ~R ......i - - - - - -
(Functionalised
benzene)
I/H20
<¥-R Cr(CO)3
ry
H
H
ra
X
_oNU oNU
ib
ON~
6 slow
yl
+ Nu ~
-.::::--- ~ ~
m
Nu
ea
lc
he
© •
fast
(-x-)
Here it may be noted that free benzene or chlorobenzene does not respond to the said nucleophilic
substitution reactions under the comparable conditions.
This aspect will be illustrated later more by taking the organometallic compounds.
th
(iv) Nucleophilic attack on the coordinated olefin:

e/
t.m
It happens so in the cases where M --+ olefin n-back bonding is less important (i.e. heavier
e
transition metals; presence of other strong n-acceptor ligands like CO) so that the coordinated
er
olefin is electron deficient. In fact NH 3 as a nucleophile can attack the coordinated olefin in
[(115_Cp~W(CO)3(112_C2H4)]+.This reaction has been discussed later (Sec. 10.12.81).
H
D. Electrophilic attack on the coordinated ligands (cf Sees. 10.12.7-8): When the coordinated ligand
becomes more electron rich, the situation arises. In fact, good metal (d) --+ ligand n-bonding will
make the coordinated ligand electron rich. This n-back bonding is favoured when the metal centre
k
is electron rich and in low oxidation state. In fact, the soft metal centres from the 2 nd and 3 rd transition
lic
series are the ideal candidates for this purpose. Such electron rich coordinated ligands are very much
susceptible to the attack by electrophiles.
C
(i) Ligand protonation: Protonation of the coordinated dinitrogen, isonitriles, unsaturated hydro-
carbons with the metal centre present in the core M(diphosphine)2 is well documented.
The metal core M(diphosphine)2 generally consists of M = Mo, W, Ru, Fe etc., diphosphine =
R 2P-CH 2CH 2-PR2 (R = Et, Ph, etc.), a good a-donor and poor n-acceptor
[M-N=N~M=N-N(H
H]2+
; cf effect of protonation on [Mo(dppelz(N 2 hJ, (Sees. 10.12.10 and 9.11)
It leads to activation of dinitrogen to mimick process involved in biological N 2-fixation.

ry
ra
ib
(ii) Ligand protonation: Ligand protonation is an important step for the electrophilic substitution
reaction on the coordinated ligand. It is illustrated below.
yl
m
11\4.~
/A 1
>..." FS03 H/S02F2
he
----~.
Fe(CO)a
(18e)
(butadienetricarbonyliron)
lc
ea
Probably, the metal centre is protonated first (cf Sec. 10.12.7; [Cp2FeH]+) followed by the hydride
transfer from the Fe-H bond to the 114-butadiene giving rise to 113-coordination and two electron
th
oxidation of Fe. It may be considered as the oxidative addition of H+ as H- to the metal centre (cf
H+ + 2e ~ H-).
e/
(iii) Electrophilic substitution on the coordinated acetylacetonate: In [M(acac)3] (M = CrIll, COllI,

t.m
Rh IlI , etc.), pseudoaromaticity is maintained in the coordinated chelate and electron delocalisation
occurs through the participation of metal d-orbital. In fact, coordinated acetylacetonate behaves like
the free benzene ring in terms of electrophilic substitution reaction. The electrophilic substitution
occurs on the central C-atom of the chelate ring. It eventually leads to replacement of the hydrogen by
e
E+(elecrophile).
er
H
/CH 3
o--c
/~, +E+
k
(acac)2M, "--.-/ /C-H

lic
o--c (slow)
"CH a
C
/ / /
o-c
LM /0'
\ /
C-H LM /0'
\
O-C
/
C-N0 2 H/Pd
-----J.~
. LM\
/ 0'
O-C
/C-NH 2
O-C O-C O-C
" "/ "
ry
O-C
0
ra
LM/ 'C-sr (X = Br)
\ /
O-C
ib
"/
yl
O-C
RCOCI
LM/ 0 "C-C-R
m
(Friedel-Crafts reaction)
\O-C/ II
he
" 0
Such electrophilic substitution reactions may involve halogenation, acylation, formylation, etc. Here
lc
it may be mentioned that the free ligand cannot experience such an electrophilic substitution reaction
under the similar condition. The optically active tris-chelate undergoes the said electrophilic substitu-
ea
tion reactions without any racemization. It supports that the coordinated chelate ring experiences the
said electrophilic substitution reaction and no ring opening and ring closing phenomena occur during
th
the process.
The electrophilic substitution on the coordinated acetylacetonate becomes favoured because of the
e/
following reasons: enolate (i.e. anionic form) of the coordinated ligand is relatively richer in electron
density compared to the protonated form of the free ligand; electron donation from the metal to ligand
t.m
n-system makes the ligand electron richer.

More examples of electrophilic substitution reactions on the coordinated ligands will be illustrated
in connection with the organometallic compounds.
(iv) Nitration on the coordinated phenanthroline ligand: Nitration of the free ligand, 1, 10-
e
phenanthroline occurs only under the drastic conditions - in presence of the mixture conc. HN0 3 and
er
oleum at 170°C. On the other hand, nitration of the ligand in [Co(phen)3 ]3+ occurs at the relatively
milder conditions - mixture of conc. HN0 3 and H2S04 at 80°C. In this way, 5-nitro-l, 10-phenanthroline
H
may be isolated from the nitrated complex when treated with edta. In indicates that in the
[Co(phen)3]3+ complex, the coordinated ligand is richer in electron density than the/ree ligand. It is
k
mainly due to the metal ~ n*(phen) electron pushing effect.

lic
[ CO (phen )3 J3+ HN03/H2S04

(Boac»
[ (.
Co 5-nltro-phen
)
3
J3+ edta ) 5-nitro-phen + [CO (edta)]-
C
(V) Chlorination on coordinated pyridine:
E. Attack on coordinated ligand leading to pseudosubstitution:

The mechanistic aspects of these reactions have been discussed in Chapter 5.
10.12.2 Activation of Coordinated Ligands and Function of Metalloenzymes
ry
Coordination with a metal centre (acting as a Lewis acid) can polarise the ligand. Thus the biomolecules
ra
(i.e. substrates) acting as the ligands are activated. The examples in this class include hydrolysis of
esters, peptides, ATP, etc. When complexation is accompanied with the anionic charge neutralisation
ib
(leading to an entropic favour through the desolvation of reactants) of the substrate (as in the case of
phosphatase activity), it favours the approach of the nucleophile in addition to an entropic favour in
yl
the hydrolase activity. These are discussed in detail in the Author's book Bioinorganic Chemistry,
m
Book & Allied, Kolkata, 2011.
he
10.12.3 Activation of Coordinated Ligands and Catalysis
This aspect has been discussed separately in Sec. 1.9.
lc
10.12.4 Activation of Dihydrogen (H 2 ) and 'C-H' Bond through Metal Ligand Interaction
ea
These aspects have been discussed separately in Secs. 10.8-9.
th
10.12.5 Activation of Coordinated Ligand and Template Synthesis of Macrocyclic Ligands

e/
This aspect has been discussed separately in Sec. 1.9.

t.m
10.12.6 Some Representative Examples of Reactions at the Coordinated Ligands

This field may cover a huge range. Some of the specific examples have been discussed in Sees. 10.12.1-5
and some specific examples involving dioxygen, dinitrogen as ligands and organometallic compounds
e
will be discussed in the next sections. Here we shall cite some more examples.
er
(a) Nucleophilic attack on the coordinated ligand: Some examples involving the hydrolytic cleavage
of the functional groups of the coordinated ligands have been discussed in Sees. 10.12.1 and 8. The
H
ligand polarisation effect is more pronounced to the site closer to the point of coordination and the
nucleophilic attack generally occurs there. However, in some cases, long range polarisation may also
k
direct the nucleophilic attack at the site far away from the site of coordination. This is illustrated in the
lic
following example.
o HO OH
C
Hydration of bis-(2-pyridyl)ketone when coordinated with Cu(lI)
(b) Electrophilic attack on the coordinated ligand: Some examples have been already discussed
in Sec. 10.12.1 and some more examples will be given in discussion with the reactivity of ferrocenes
and organometallic compounds (Secs. 10.12.7-8).
(c) Reaction of diketone with hydrogen sulfide: Free diketones react with H 2S to give upto the
monothio derivative. But the monothio derivative when coordinated with Pt(II) can react with H2S to
give the dithioketone derivative.
__ H_2S_----:i~~ yy
ry
(No further 0 S
reaction)
ra
ib
211(
yl
o S
m
he
Here coordination by the carbonyl oxygen polarises the 'C-O' bond sufficiently to allow the nucle-
lc
ophilic attack on the carbonyl carbon. There is another point to favour the reaction through the stabilisation
of the product by soft-soft interaction. Thus the choice of Pt(II) complex is quite important as it offers
ea
the dual roles: polarisation the 'C-O' bond and stabilisation of the product. Thus, the situation may be
compared with the template effect.
th
(d) Participation of the coordinated amino acids in aldol condensation: When an amino acid
remains coordinated with the metal centre, the a-C-H bond is sufficiently polarised to introduce the
e/
protonic character in the hydrogen of the a-C-H bond. In fact, in presence of OH-, the proton
t.m
abstraction may produce a carbanion centre at the a-C.

In fact, [Cu(gIY)2] reacts with acetaldehyde in presence of OH- to give a complex of threonine. This
type of aldol condensation may be generalised for the other amino acids also. This may be considered
as a template synthesis.
e
o~c-o e~
er
N2_~ __ ~ °Il)
H
H
+OH- ,,/ I H CH 3- C - H
I /C~ ~
k
H C-N O-C (H 2 0)
2 ~
lic
H2 "0
C
H
o~ H2 / OH
C1-0" /N-C "" /
H2C-~ /'.
1 "'"
Cu
O-C~
C-H
CH 3
2 0
[Cu(gly)(thr)]
(e) Participation of the coordinated carbonyl group in Schiff base (i.e. imine) formation: Schiff
base formation reaction is acid catalysed.
"'~N-R
'"
/
C====O
/V
C ====OH -------:l.~ -H 30+
•
'"
/C=N-R
ry
(Schiff base)
ra
The basic step of the above reaction is the polarisation of the 'C-O' bond through protonation.
ib
This subsequently favours the nucleophilic attack on the carbonyl carbon. The carbonyl group is also
activated in the same way when it remains coordinated with an electron withdrawing metal centre. This
yl
is illustrated in the following example. This may be described as a template effect.
m
he
Cu2+,OH-
..
lc
ea
th
e/
t.m
e
er
+ 2R-NH 2 (Imino complex)

H
(f) Intramolecular condensation within the coordination sphere leading to Schiff base:
Coordinated NH 3 ligand may participate in such condensation reactions, if the cis-ligand can provide
a carbonyl group which is already activated.
k
lic
,;/'0
o-c ~O
C
(HN)CO/ ~C~
3 4 '0+
CH 3
H )
Protonic hydrogen
(g) Peptide linkage formation within the coordination sphere: It is illustrated below where
[Co(en)2(glyOR)]3+ reacts with free glyOR (say ethylglycinate) to produce a peptide linkage.
ry
ra
It may be mentioned that hydrolysis of the coordinated amino acid ester (discussed in Sec. 10.12.1)
also occurs in the same way.
ib
(h) Reactions of the activated amines remaining coordinated: NH 2-R coordinates with its lone
yl
pair. Thus, apparently the coordinated amine should not be able to act as a nucleophile. But if the metal
centre is a strong Lewis acid (e.g. trivalent M 3+ like Co 3+, Rh 3+, etc.) then the hydrogen of the N-H
m
bond becomes sufficiently acidic and through this proton loss, the coordinated amine can act as a
he
nucleophile. This has been already illustrated in the intramolecular condensation leading to Schiff
base.
lc
ea
H H Me H
""'/ ""-/
/N--CH2 ~ /N--CH2
th
(enb Rh" I
Me-I
-HI • (en)2 Rh" I
e/
N--CH N--CH
/""- 2 /""- 2
t.m
H H Me H
Protonic H
In this way, substitution in all the three chelate rings may occur.
e
er
10.12.7 Reactivity of the Cyclopentadienyl Rings of Ferrocene

(A) Electrophilic Attack: Cyclopentadienyl rings of ferrocene [Fe(1l5-Cp)2] are aromatic in character.
H
(i) Acetylation (Friedel-Crafts reaction): The reactions are:

k
o 0
lic
II II
~C-CH3 ~C-CH3.
C
o
II
+ CH 3--C--CI Fe +
~
(mono substituted product) (1, 1'-disubstituted product)
(Major product) (Minor product)
The 1, I-disubstituted product is negligibly small
ry
1-1 '-disubstituted product :
1, 1-disubstituted product = 60: 1
ra
ib
(1, 1-disubstituted
yl
product)
m
+
In the said Friedel-Crafts reaction, the electrophile CH 3 - C=O (acetyl cation) is generated as
he
follows:
CH 3COCI + Alel 3 ~ AICI:; + CH 3 CO+

lc
Acetyl group is an electron withdrawing group. Hence its entry will deactivate the ring to disfavour
ea
the entry of another acetyl group through the electrophilic substitution reaction. Thus, formation of
1, I-disubstituted product is very much disfavoured. But to explain the predominance of the monosub-
stituted product compared to the 1, l'-disubstituted product, it is to be considered that the electronic
th
effect of one ring (where the acetyl group enters) is transmitted to the other ring through the metal
centre. Otherwise, acetyl group present in one ring would not be expected to deactivate the second ring.
e/
Thus, the actyl group can deactivate both the rings but definitely it deactivates its own ring more.
t.m
• If disubstitution occurs at all in the same ring, it will occur at the ortho-positions .
• 1, 1'-disubstituted product gives only one compound (without any isomer). It proves the free
rotation (cf. Fig. 10.11.3.1) of the Cs rings in [Fe(Cp)2] in solution (i.e. the energy barrier for this
rotation is too small). In absence of rotation, it would give three isomeric products.
e
er
o
II
o-
H
c---- R
....... R
C
k
II
lic
o
C
Fig. 10.12.7.1 Three possible isomers of I, I'-disubstituted products of [Fe(CphJ in absence of rotation around the
Cp-Fe-Cp axis.
5 ) ] (CH 3 CO)20
[ Fe ( 11 -Cp 2 -----~) Only monoacyl product.
+H 3 P04
If acetylation is carried out by a mixture of phosphoric acid anhydride and phosphoric acid, it gives
the monoacyl product only. It occurs so because of the two probable reasons: generation of the required
electrophile (CH 3CO+) occurs to a very small extent (compared to the reaction mixture CH 3COCI +
AIC1 3) and the CH 3CO group being electron withdrawing in natrue deactivates the further acetylation
process.
(ii) Alkylation (through the Friedle-Crafts reaction): It leads to dialkylation homoannularly. Alkyl
group being electron pushing in nature favours the further electrophilic attack (cf CH 3CO group
deactivates further the electrophilic attack).
ry
(iii) Aminomethylation through Mannich reaction:
ra
ib
yl
[Fe(l1s-CP)2] + CH 20 + HNMe 2 C~3~~:H )
m
(Mannich Reaction)
he
[(1l5-C s Hs )Fe(l1s-CsH4CH2NMe2) ]~[ (115_CsHs )Fe(l1s-CsH4CH2NMe;I-)]
lc
ea
In Mannich reaction, the effective electrophile (E+) is generated in the following reaction.
eft c;
th
R",.(") I
e/
+ H-C-H ::;;:=: N-C-H

R/ I
t.m
Thus the cation of the imminium salt is the effective electrophile (E+) that leads to the electrophilic
substitution on the Cs-ring.
e
• Here it may be mentioned that benzene cannot undergo Mannich reaction but the Cp-rings of
er
[Fe(Cp)2] can undergo the reaction. It indicates that the Cp-rings in [Fe(Cp)2] are more electron
rich than the benzene ring. Thus in this regard (i.e. in terms of electron density in the ring), these
H
Cp-rings of [Fe(Cp )2] are comparable to the thiophene and phenol.

The product dimethylaminomethylferrocene is an important starting material for the preparation of
many other derivatives.
k
lic
C
(iv) Metallation: It can be readily done by using RLi (e.g. n-BuLi). It may be noted that benzene can
also experience the metallation in the same way.
<0) + n-BuLi - - - - @----Li (phenylithium) + C4 H,o

{C6H @-H9+ H+;

2+
Mercuration
6+ Hg ~ +
CSH S + Hg(OAc)2 ~ CsHs-Hg - OAc + AcOH
ry
~I ~H9(OAC)
~Li ~Li
ra
12 Hg(OAc)2 n-BuLi n-BuLi
ib
Fe .. Fe .. Fe .. Fe .. Fe
~ ~
yl
Jrl JrH9(OAC) JrLi
m
he
This easy metallation process supports the typical aromatic systems in the Cp-rings offerrocene.
Thus the Iithio-derivatives obtained may be used in many reactions to prepare the ferrocenyl
derivatives. lc
(v) Nitration and halogenation: These cannot be done directly as the electron rich Cp-rings will
ea
undergo oxidative cleavage or the ferrocene may be oxidised to ferricenium (17e system) in presence
of the oxidising agent like conc. RN03, Br2' etc. However, the nitro or halo derivatives offerrocene may
th
be obtained from the lithio derivatives as discussed here.

e/
n-BuLi
r [(l1S-CsHs)Fe(l1S-CsH4Li)] .....1 - - - - - [Fe(l1 S- Cp)2]

t.m
co2 ~P4
[(l1S-CsHs)Fe(l1S-CsH4C02H)] ~ [(llS-CsHs)Fe(l1S-CsH4-N02)]
o
e
-£
B(OR)3
z
I Fe/HCI
er
(hydrolysis)
H
k
lic
C
[(l1S-CsHs)Fe(l1S-CsH4-1)]
~ Mg
(vi) Hydrolysis of a-ferrocenylcarbinyl acetate: The hydrolysis reaction operates through the
formation of carbonium ion. Here it may be mentioned that this hydrolysis rate is even much faster
than the hydrolysis rate of triphenylmethyl acetate which also passes through the carbonium ion mecha-
nism. This rate data indicate that ferrocene can stabilise the carbonium ion.
ry
OAc OH
I I
ra
~r-R ~r-R
ib
~
yl
Fe Fe
1
~
m
electron
flow @
he
Representing the
filled weakly bonding
molecular orbital enriched
with the character of
metal orbitals.
lc
ea
The stability of carbonium centre is argued to be due to the overlap between the filled metal orbital
(i.e. filled weakly bonding molecular orbital) and the vavant p-orbital ofthe carbonium ion centre. This
th
argument of stabilisation of carbonium ion is supported by the fact that vinylferrocene is extremely
reactive to the addition of weak acid like CH3C0 2H, HN 3 across the double bond. The process goes
e/
through the formation of the carbonium ion centre.

t.m
e
er
H
k
lic
(X-= N;, OAc- )
(vii) Electron releasing effect of the ferrocenyl group: Ferrocenyl group shows a very powerful
C
electron pushing inductive effect. This is supported by the following fact:

• aminoferrocene) aniline, (base strength).
• ferrocene carboxylic acid ( benzoic acid, (acid strength).
• [(lls-CsH4-NH 2)Mn(CO)3] ( C 6Hs-NH2 ( [(llS-CsHs)Fe(lls-CsH4-NH2)]
(Base strength order)
It indicates the order of electron withdrawing power of the groups:
Mn(CO)3 ) C 6Hs ) (llS-CsHs)Fe
It is also further supported by the fact that compared to ferrocene, [(llS-Cp)Mn(CO)3] is less susceptible
to the electrophilic substitution.
C 6H s-NH 2 > [(1l6-C 6H s-NH 2)M(CO)3], (M = Cr, Mo, W) (Base strength)

C 6H s-C0 2H ( [(1l6-C 6H s-C0 2H)M(CO)3], (acid strength)
It indicates that the M(CO)3 group is electron withdrawing.
Mechanistic path of electrophilic substitution: Benzene vs. Ferrocene

The electron rich character (i. e. electron donor property) of ferrocene is supported by the fact
ry
of easy electrophilic substitution reaction.
ra
kacetylation ==> ferrocene : benzene = 106 : I
kmercuration ==> ferrocene : benzene = 109 : 1
ib
The favoured rate for ferrocene is argued based on the higher stability of the a-ferro-
cenylcarbonium ion. The electron of filled metal orbitals (i.e. weakly bonding electrons) may
yl
also interact with the electrophile (E+). In fact, ferrocene may be protonated at the metal centre in
m
a strong acid media to give [(lls-Cp)2FeH]+.
, Fe
ea
lc
he
~
th
e/
Steps for electrophilic substitution on benzene ring

t.m
~ HE HE HE
+X ---- U----U
W X X+
0 slow
e
::::..... 1 + E+ (electrophile) ~
er
H
E
III
H E
6 0
k
lic
fast (planarity is lost,

H+ + 4
distorted to boat
C
form)
10.12.8 Reactions of the Coordinated Ligands in Organometallic Compounds

A. Nucleophilic attack on the unsaturated hydrocarbons acting as the good donor ligands
Unsaturated hydrocarbons possess the 1t-electron cloud and consequently such electron rich com-
pounds repell the approach of the attacking nucleophile. In fact, such unsaturated hydrocarbons (in free
state) are not active towards the nucleophile. However, when they remain coordinated as the donor
ligands, the 1t-electron flow from the ligand to metal through a a-type or JJ.-type interaction will make
the ligand relatively more electron deficient. This ligand to metal electron flow will be favoured when
the metal centre is relatively in higher positive oxidation states and/or coordinated with other good 1[-
accepting ligands. The electron withdrawing tricarbonyl metalfragment M(CO)3 (M = Cr, Mo, W) can
activate the unsaturated hydrocarbon ligand. Thus, the unsaturated hydrocarbons acting as the 1i-
donor ligands are activated towards the nucleophilic attack. The susceptibility to the nucleophilic
attack in the 18e-cationic complexes has been found to follow the following order.
C>@ ©
ry
I >( > > [Q]2-» ~ - > ~ >@ >
ra
ib
From above series expressing their nucleophilic susceptibility order, we can conclude as follows:
• Even hapticity vs. odd hapticity: Ligands with even hapticity are more reactive than those with
yl
odd haptacity; it is reasonable as the even hapticity ligands (except cyclobutadiene C4H 42-) are neutral
m
while the odd hapticity ligands. (except tropylium, C 7H 7+) are anionic; the electron rich anionic ligands
will resist the approach of the'nucleophile more.
he
• Open ligands vs. closed ligands: The open ligands (i.e. acyclic hydrocarbons) are more suscep-
tible to the nucleophilic attack than the closed ligands (i.e. cyclic hydrocarbons). Attack generally
occurs at one end of the acyclic ligand. lc
• Order of nucleophilic attack: If in a complex, there are different types of unsaturated hydrocarbons
ea
as the ligands, then the given series can predict which ligand will experience the nucleophilic attack
first.
th
All these predictions or rules (predicted by Green, Davies and Mingos, 1978) are formulated from
the kinetic considerations. These are illustrated in the following examples:
e/
t.m
(i)
e
Nu- ~
er
H
(Nu- = OMe-, SMe-, CN-, H-)

k
> © »<t-. Thus in the above

lic
Reactivity order of the unsaturated hydrocarbons is: (

C
reaction, the relatively unreactive ligands, i.e. benzene and allyl-group remain as the spectator
ligands.
l+ ~ lO
~
(ii) [(1l5-Cp)Fe(llS-C sHs)]+
Fe + Nu-
(Nu- = -OMe)
~ Fe
~H H
YI "'CO NU~I "'CO (1l5-Cp)Fe

CO CO
Here, the more reactive olefinic moiety reacts while the more unreactive cyclopentadienyl group
remains as the spectator ligand. The second reaction proves that C6H6 is more reactive than Cp-
towards the nucleophile.
(iii)
ry
+ Nu-
ra
ib
yl
m
CH 2
(iv) C' 2(Ph 3 P)pt----11
he
CH 2
For lc
Nu- = Et 2 NH, i.e. product is, [CI 2 (Ph 3 P)Pt- -CH 2 CH 2 - +NHEt 2 ]
In fact, hydration of alkene catalysed by the metal ions may be considered as the nucleophilic
ea
attack by H 20 on the coordinated alkene.
th
H H
I I
e/
LPd-C-C-OH + H +, (ct. Wacker process)

I I
t.m
R R
e
The neucleophilic attack may occur by a coordinated H 20 molecule (that may have the M-OH
er
character due to the Lewis acidity of the metal centre and the metal bound OH group can act as a better
nucleophile).
H
k
lic
C
Hydration of alkene and alkyne is catalysed by Hg2+ and the reaction pathway probably involves
the nucleophilic attack on the coordinated alkene or alkyne.
Note: See (I) of this section for more examples of nucleophilic attack on the coordinated olefins.
(v) Benzene ring is generally inert towards the nucleophilic attack but it can be activated when it
becomes attached with the electron withdrawing tricarbonyl moieties like M(CO)3 (M =Cr, Mo, W).
This aspect has been already illustrated in Sec. 10.12.1. Some additional examples are given below.
CI
Nu
~CI + Nu- ~
-CI-
.. ~NU
ry
Cr(CO)3 Cr(CO)3
(Tl 6-coordination)
Cr(CO)3
ra
(115-coordination) 12 , H2O
(Nu- may be R-)
ib
(NVE = 18; OS = 0)
yl
H @-NU + Cr(lll)
m
Nu
he
.. .. @-NU
1>
I/H 2O
+ Nu- + Cr(lIl)
lc
ea
Cr(CO)3 Cr(CO)3
th
(vi) 115-Cp- is also very much inert towards the nucleophilic attack (cf Sec. 10.12.7) but it is activated
when it is present in the cationic complexes. In fact, such complexes respond only to the very strong
e/
nucleophiles.
Ph
t.m
---~-H
(Tl 4 -coordination)
e
Conjugated
alkene
er
+ LiPh ~ Co + Li+
~
H
(18e. OS = +1)
k
lic
(18e, OS = +3)
C
H H
H
H H
Nu
Nu
(vii)
(Tl 4-cyclohexadiene Fe"(CO)3

complex) (18e)
(Tl 5-cyclohexadienyl complex) (114-coordination)
H- abstraction by Ph 3C+ from a cyclic diene places the fifth C-atom in conjugation (i.e. 4e donor
11 4 ~ 6e donor 11 5) and the metal centre is formally oxidised by two unit.
B. Electrophilic att'ack on the coordinated unsaturated hydrocarbons
This is favoured when overall charge of the complex is zero or negative and the metal centre is electron
rich. The electron. rich metal centres (i.e. low oxidation state and late members of the transition series)
temporarily may accommodate the attacking electrophile (E+) by using the filled nonbonding or weakly
ry
bonding orbital. In fact, in IFe(Cp)2]' the electrophile is first accommodated on the iron centre (cf Sec.
10.12.7).
ra
• In [Fe(1l5-Cp)2], the aromatic Cp- ring expriences an electrophilic attack in Friedle-Carfts reac-
ib
tion. These have been discussed in Sec. 10.12.7 separately.
• In the cyclobutadiene complexes, the aromatic moiety cyclobutadiene ligand can also experience
yl
the electrophilic substitution reactions.
m
~I
he
-~+ lc FeCI 2 + 6CO
CI
ea
Fe(CO)3 (18e, OS = +2)
th
o
e/
+
II
CH 3- C - C I
t.m
(Friedel-Crafts
reaction)
Fe(CO)3 Fe(CO)3
e
~CI
er
Hg(OAc)2
+ NaCI
H
Fe(CO)3 Fe(CO)3
k
lic
• Protonation on 1, 3-diene ligands:
~
C
[Fe(CO)s! + C4 Hs - Fe(CO)3 + 2CO
(1l3·coordination)
~ ~r""
3
CH
CI- _______
OC-Fe"-CI
(NVE = 16) o/"'CO

~Fe(COh + H++ X- - b-Fe(COlY'

(18e, as = 0) (18e, as = +2)
4
(11 - cydohexadiene complex) (113-coordination)
ry
In these protonation processes, H+ (as an electrophile) first binds with the nonbonding/weakly bonding
orbital of the metal centre (cf [(Cp)2Fe] + H+ ~ [(Cp)2FeH]+; Sec. 10.12.7. Then H- transfer from the
ra
metal centre (i.e. 2e oxidation of the metal centre) to the 114-ligand leads to the 113-ligand. However,
both the 11 3- and 11 4- forms of the ligand act as the 4e donor ligand.
ib
yl
c. Hydride (H-) addition/transfer:
l
m
H R' +
(115_C5H5)(CO)2Fe~
he
BF; + CHPh 3
H R·
lc
(triphenylmethyl cation acts as a H- abstracting agent and H- abstraction causes a 2e oxidation of
the metal centre. BH4- acts as a H- donor)
ea
The above reaction represents the hydride abstraction from the alkyl ligand to produce an alkene
complex.
th
Note: The above reaction may be compared with the olefin insertion and p-elimination process.
e/
H
t.m
(115-coordination)
e
er
Mn(CO)3
H
Note: This H- addition reaction may be considered as the nucleophilic attack on the coordinated
benzene.
k
lic
C
(iii)
1)- Feo (CO)3
+Ph3C+, - Ph 3CH
- - - - - - - - 3. .
(H- abstraction)
~ (1l5-cyclohexadienyl complex)
(1l5: 6e donor)
(11 4: 4e donor)
(114-cyclohexadiene
complex)
H- abstraction places the fifth C-atom in conjugation and FeD is formally oxidised to Fell. A similar
situation is illustrated in the following reaction.
H3C~ FeO(CO)3
114-butadiene
ry
coordination by
1, 3-pentadiene (CsH a) 115_pentadienyl complex
ra
Similarly, H- abstraction from T1 6 -cyclohexatriene coordinated to Cr(CO)3 gives the
T1' -cycloheptatrienyl (i.e. tropylium) complex. In the same way, T1 6-cyclooctatriene can be converted
ib
into T1' -cyclooctatrienyl.
yl
D. Ligand protonation (cf. Sec. 10.12.1 D)
m
he
lc
ea
th
e/
t.m
The probable mechanistic path is as follows:

e
er
H
k
lic
+
CI /CI
C
(iii) ('lcac)pt( H+
(acac)Pt
~
CH 2 ~
""'CH2
-H+
H/
'\C=O
H
)\ OH
E. Nucleophilic attack on the coordinated CO (cf. Sec. 10.12.1):

(i) Attack by OH-:
8-~ 8+ 8- 06+ n
M + C=O:--..M-C==O~M=C=O
(NU (NU
ry
ra
-OH
-----3.~ [(OC)4FeH]- + HCO:J-
ib
yl
m
Probable transition state for ~-elimination
followed by the attack of OH- on CO 2 released.
he
(ii) Attack of H- (from NaBH4) on coordinated 'CO'
[)0_~. M_C~O lc ~
-
M-CH~31
H - (i) + H (i) +H -
ea
M-CH 20H •
" (ii) + H+ (ii) -OH-
H
th
e/
]~[ (OC)4 Fe --- C<: r

t.m
[Fe(CO)5
]~[ (OC)5Cr --- C<: r

e
[Cr(CO)6
er
Note: Depending on the condition, CO group may be converted into different groups like 'CHO',
H
'CH 20H' and finally to CH 3•

(iii) Preparation of Fischer-carbene: ~
k
lic
[(OC)5W(CO)] PhU' {(OC)52c<:J -~:-+OC)5W=C(::]

C
(iv) Interaction with lithium alkyls (R- Li+)
[Mn(CO)6r + R-U+ ----+OC)5Mn---C(:]

[Fe(CO)s] + WLi+ ---{OC)4Fe-c(:r
(V) Interaction with amines:
ry
ra
-
+
R-NH 3
1 +R-NH 2
(excess)
ib
yl
m
(vi) Interaction with O-atom:
he
0
~ RiJ-CZ -
lc / -C0 2 •
(OC)4Fe_C~ • (OC)4F~~ [(OC)4FeNMeJ
ea
i.e., [Fe(CO)5l
(cf. [Fe(CO)5l + OH- ~ )

"0°
Me 3 N
th
(~-elimination)
e/
(vii) Attack by alkoxide (RO-)

t.m
[(Ph 3P)2 Ir (CO)3 J+

CH 3 0
H'
[(PPh 3 )2(OC)2 Ir - c (0 ]
OCH 3
e
This reaction is important for the synthesis of carboxylic acids and esters.
er
F. Nucleophilic attack on coordinated NO:

H
0
[Fe (CN) 5\lNO)]2- + OH- ~
slow [(NC) 5 Fe - N '/ \ ]3- (fast) OH-
(-H 0 ) )
[Fe(CN) 5 (NO 2 )J4- ; ( see S ec. 9 .6 .3)
k
(Nitroprusside) OH 2
lic
G. Nucleophilic attack on coordinated isocyanides (cf. Sec. 10.12.1):

C
It leads to Fischer carbene type complex which can be represented as follows

,NHR
/;/
M=....::....::..C
~. y
H. Nucleophilic attack on coordinated nitrile (ct. Sec. 10.12.1):
{\ ~3- H /R
M-N=C-R + H-Y~M-N=C"
Y
ry
ra
ib
I. Nucleophilic attack on the coordinated olefin (ct. Sec. 9.17.5): It is illustrated here.
yl
m
he
lc
ea
th
e/
t.m
Zeise's salt anion, [Pt(C 2 H 4 )CI.:d- on standing slowly gives CH 3CHO through the nucleophilic attack
by H 2 0 on the coordinated ethylene. Conversion of C 2H 4 into CH 3CHO by the Pd-complex (L:f
Wacker Process) is also involving the nucleophilic attack on the coordinated ethylene (c.f Sec. 10.l3.6).
e
Oxymercuration is a useful reaction to introduce the OH, OAc, OR groups into the unsaturated
er
system. The reaction pathway involves the nucleophilic attack on the olefin coordinated to Hg(lI).
Hg(OAc)2 ~ Hg(OAc)+ + OAc-
H
"" II
k
c/ '
lic
+ Hg(OAc)+
/'C""
C
(trans-addition)
Hg(II) calalysed aquation of alkenes and alkynes probably passes through this pathway.
J. Intramolecular C-H activation leading to cyclometallation: These aspects have been already
discussed in Sec. 10.8.2. The 'M-C' bond formation through the intramolecular hydrogen transfer is
also illustrated below:
ry
ra
~,
2 ~ + 2[PdCI 4] 2- -----I,..
-2HCI
+ 4CI-
ib
©
yl
m
he
(azobenzene)
10.12.9 Characteristics of the Dioxygen Complexes, i.e. O2 as a Ligand (cf. Secs. 1.7,9.13,
lc
10.12.9,12.1.17; and Sec. 14.7.5 of Vol. 3): Reactivity of Coordinated Dioxygen:
ea
Activation of O2
It is well known that free dioxygen (triplet state) camnot react with many organic molecules (which
are singlet) due to the presence of a kinetic barrier, i.e. triplet-singlet reactions are kinetically forbidden.
th
However, the coordinated dioxygen is kinetically more reactive than the free dioxygen. Coordinated
e/
dioxygen may remain in different states like singlet dioxygen, superoxide or peroxide. This makes the
coordinated dioxygen active. This aspect has been discussed in detail in the present author's book,
t.m
Bioinorganic Chemistry, Books & Allied, Kolkata, 2011.

Let us consider the thermodynamic aspects of dioxygen as an oxidant.
02+4H++4e~2H20, E o =1.23V(pH-0), =+0.81V(pH-7).

e
Thus it is evident that O 2 is a very powerful oxidising agent (thermodynamically) even at neutral pH.
er
But the 4e-transfer at a single step is the rarest possibility. Hence, the thermodynamic aspects of
1e-transfer steps are to be considered.
H
O 2 + e ~ 02" (superoxide), Eo (pH - 7.0) = -0.35 V

02- + 2H+ + e ~ H20 2, Eo (pH - 7.0) = + 0.90 V
k
lic
H 20 2 + H+ + e ~ H20 + OH, Eo (pH - 7.0) = +0.38 V

OH + H+ + e ~ H20, Eo (pH - 7.0) = 2.31 V
C
It is evident that the first-step leading to 02- is thermodynamically unfavourable. This is why, O2
needs a very strong reducing agent to overcome this barrier. In fact, this thermodynamic barrier
protects many oxidisable species. However, in the presence of metal ions, the complexation may
activate 02' O2 can bind in the following ways (see Sec. 9.13 for details of metal-dioxygen bonding).
(11 1- 0 ) 0
2~
M-O
(e.g. Hb-02 ) (e.g. M = COlli)
In these complexes, O 2 remains very often as ° or 0i- and thus the thermodynamically uphill
step for the formation of Oi is overcome. The species
2-
°2- or 0i- (remaining coordinated) does not
experience any such thermodynamic barrier for their oxidising activity. This leads to the activation of
dioxygen through complexation.
Hemoglobin (Hb) and myoglobin (Mb) bind O 2 reversibly giving rise to the FeIII-Oi adduct. Many
Co(II)-complexes bind O 2 to give the binuclear complexes bearing the J.!-Oi or J.!-oi- linkage.
ry
ra
ib
yl
m
Jl-O; or Jl-O:-
he
lc
ea
Some common examples to illustrate the enhanced reactivity of the coordinated dioxygen are
th
given below.
e/
t.m
e
er
H
k
PPh s
lic
OC,i / 0 *
[Ir I (CO)(CI)(PPh s)2] ~ \r I
C
Vaska's complex CI/I"o'

PPh s
10.12.10 Characteristics of the Dinitrogen Complexes, i.e. N2 as a Ligand (cf. Secs.1.7,

9.11 and 12.1.17): Reactivity of the Coordinated Dinitrogen: Activation of N2
(A) Inertness of N2 : Free dinitrogen (N 2 ) is tremendously inert due to: (i) very high bond energy (ca.
950 kJ mol-I); (ii) very high energy gap between the HOMO and LUMO makes N2 nonpolarisable and
resistant towards the electron transfer process; (iii) LUMO being antibonding in character restricts it to
take up the electron, (iv) HOMO being a-bonding in character makes the electron release process
difficult; (v) nopolarisable character disfavours it to adopt a polar transition state required in the
nucleophilic or electrophilic attack on N2'
However, when N 2 binds as a n-acid ligand, it becomes relatively more active. Accumulation of
electron density in the LUMO (antibonding in character) through its n-acceptance property, makes the
'N-N~ bond of the coordinated N 2 weaker (streching frequence drops to 2200 - 1850 cm- l from
ry
2331 cm- I of free dinitrogen). The electron rich character of the coordinated N2 makes it a better
base. In fact, the reduced bond energy and increased basicity in the coordinated N 2 are basically
ra
responsible for the enhanced reactivity of the coordinated N 2. Biological nitrogen fixation by the
nitrogenase enzyme probably uses the property of the enhanced reactivity of the coordinated N 2. These
ib
aspects have been discussed in detail in the author's book, Bioinorganic Chemistry, Books & Allied,
yl
Kolkata, 2011.
(B) Preparation of dinitrogen complexes: This aspect is discussed in Sec. 9.11.
m
(C) Ligating efficiency of CO vs. N 2 : Apparently, in terms of kind, N2 is similar to CO and they are
he
the isosteric species. In fact, both of them can act as the n-acid ligands. But, CO is a better a-donor
ligand and also a better n-accepter ligand than N 2.
This can be explained by considering the MO energy diagrams of CO and N 2 (ef Chapter 9, Vo1.2).
lc
In CO, because of the difference of electronegativity between the combining atoms, the HOMO is
ea
practically remaining as a NBMO which is primarily located on C. The lone pair of this HOMO is
used for 11 1- a-donation. In N 2, the HOMO is a a-BMO. Thus, this tightly bound electron pair is not
th
suitable for a-donation. Besides this, this HOMO is not suitably oriented for TIl-mode of coordination.
However, it may coordinate in the ,,2-mode (Sec. 9.11).
e/
The LUMO (x*) of CO is primarily located on the C-end of CO and it is suitably oriented for
n-acceptance of the metal electron cloud in the linear TIl-mode of coordination. The higher
t.m
electronegativity of 0 further favours the electron flow from the metal to the ligand CO. In N 2, the
LUMO is also n*-LUMO but it is not polarised to any end (ef in CO, n*-LUMO is mainly concentrated
to the C-end which is utilised for a-donation) to favour the n-bonding interaction with the metal d-
orbitals. Moreover, because of the absence of any electronegative heteroatom, the electron flow towards
e
the ligand cannot be additionally favoured (ef the role of 0 in CO).

er
These factors discussed above make N2 a poorer ligand than CO. In fact, N2 can only act as a
poor x-acceptor ligand with almost no a-donor propert)'. It explains the relative instability of the
H
carbonyl dinitrogen complexes, [Cr(CO>s(N 2)], [Cr(CO)4(N 2)2] compared to that of the carbonyl
complex [Cr(CO)6]' In fact, in the presence of so many good x-acceptor ligands like CO, dinitrogen
k
fails to act as a 7t-acceptor ligand in the competition. However, in presence of sufficient number of
lic
good a-donor ligands or weak n-acid ligands, N2can show its n-acidic character to stabilise the complex.
The relatively stable complexes like [Ru(NH3)S(N2)r~+, [MO(CO)3(N 2)(PCY3)2] (Cy = cyclohexyl)
C
illustrate the prediction.

In fact, among the isoelectronic species like CN-, CO, NO+, N 2, dinitrogen is the homonuclear
diatomic species (i. e. no electronegativity difference) while the others are the heteronuclear diatomic
species having the MO energy level diagram as in CO.
(D) Increased reactivity of the coordinated N 2 : Some examples to illustrate the increased reactivity
of coordinated N2 are given below.
(i) Coordinated N 2 is a better ligand due to its increased basicity. In fact, [Ru(NH 3)s(N 2)]2+ (prepared
first by Allen and Senoff in 1965) can easily produce a binuclear complex.
[(H 3N)sRu(N 2)]2+ + [(H 20)Ru(NH 3)s]2+ ~ [(H 3N)sRu-N 2-Ru(NH 3)s]4+
(ii) Electrophilic attack on the coordinated N2 is also known.

[(dppe)2W (N 2)2] + PhCOCI-7 [(dppe)2CIW(NNCOPh)] + N 2
dppe = Ph 2PCH2CH2PPh2 [1, 2-bis(diphenylphosphino)ethane] (a good a-donor ligand with a
poor x-acceptor property)
Here the electrophile is PhCO+. In some cases, H+ can also attack the coordinated N2
ry
" " _ w _ / H]2+
n...
.. ~
ra
[M - N=N-------7M=N - N'\H ; in general, N===N F(electrophile)
ib
[(dppe)2 M (N 2)2] (e.g.::" HI) >[ (dppe)~X2M==NNH2 J+ N2; (M = Mo, W)
yl
In fact, coordinated N 2 with the M(phosphine)4 or M(diphosphine)2 core is quite reactive (ef
m
good a-donor property and poor n-acceptor property of diphosphine favour the n-acceptance of
N2). The diphosphine is: R2P(CH2)2PR2 (R = Ph, Et, etc.) (ef Sec. 10.12.10).
he
(iii) Mimicking the nitrogenase activity:
cis- [ (PhMe 2P)4 Mo (N 2 )2 ] H+ x- [

-~2) )
(PhMe 2P 4XMo (NNH 2 )
lc J+ ~2NH;
H+
+ Mo(VI)-product
ea
In fact, half of the coordinated N2 in eis-[M(N2)2(PMe2Ph)4] can be converted into NH 3 on
treatment with H 2S04 in methanol. Thus the coordinated N2 is more easily reduced to NH3 • It
th
mimicks the nitrogenase activity.

e/
[ MoCI 3(thf)3J _N_a_-H..=:...-gO_fM---=;g---+) trans-[MoO (dppe)2(N 2)2] + 3CI- + 3thf

excess dppe, N 2
1
t.m
8H
+
2NH; + N 2 + Mo(VI)-Product
e
Na-Hg
er
3cr, 3 thf
H
Ti(II)-alkoxides complex with dinitrogen that may be reduced to NH 3 or N 2H 4 through the

electrophilic attack on the coordinated N 2.
k
[Ti(OR)4] + 2e~[ Ti (OR)2] + 2RO-

lic
[ Ti (OR)2 ] + N2 ~[ Ti (N2)(OR)2 J~[ Ti (OR)2 (N2) r-~[ J-

C
Ti (oRh (N2)
14H + 1 6H +
[Ti(OR)2]+N 2H 4 [Ti(OR)2]+2NH 3
Ti(OR)2 again may be recycled.

All these support the fact that coordinated N 2 is more reducible.
(iv) Strong nocleophile may also attack the coordinated dinitrogen.
ry
(v) Radicals may also attack the coordinated N2.
ra
[(dppe)2 Mo (N 2)zJ ~~~ >[(dppe)2 Mo (X)(N 2)] + .R~[(dppe)2Mo(X)(NNR)J
ib
yl
10.12.11 Characteristics of the Dihydrogen Complexes, i.e. H2 as a Ligand (ct. Sec. 9.12):
Reactivity of Coordinated H2 : Activation of H2 (ct. Secs. 1.7, 9.12)
m
(A) Chemical inertness of "2: Dihydrogen (H 2) is widely used for reduction and hydrogenation
he
reaction, but H 2 is not quite reactive because of its high bond energy. For activation, it needs very
often catalysts. For example, H 2 cannot reduce even an acidified KMn04 solution at an appreciable rate
but in presence of a catalytic amount of metal ions like Cu 2+, the process goes on. This lack of
lc
reactivity of H 2 can be realised from the following endothermic processes.
ea
• Homolytic cleavage: H2 ~ 2H, ~H ::::: 432 kJ mol- 1 (measuring bond energy)
• Heterolytic cleavage: H2 ~ H+ + H-, ~H ::::: 139 kJ mol- 1
th
These thermodynamically disfavoured processes can be overcome in presence of catalysts, espe-

cially metal complexes. These are illustrated below.
e/
(B) Activation through oxidative addition (i.e. favouring the homolytic cleavage): This aspect
t.m
has been already discussed in Sec. 10.6.4. H 2 binds with the coordinatively unsaturated metal com-
plexes giving rise to two possibilities: dihydrogen complex (1l2-H 2) and cis-dihydrido complex.
...
.. H
I
H
e
Mn+ - - - j i.e.,
I
I
er
I
I
H I
'H
H
(Dihydrogen complex) (1l2-H 2 ) (Dihydrido complex)

i.e. (nonclassical complex)
i. e. classical complex
k
"2
lic
(C) Binding scheme for as a ligand: Binding of H 2 as a ligand is illustrated in Fig. 10.12.11.1.
H2 acts as a 1t-acid ligand. It donates the a-bonding electron and receives electron from the metal
C
d-orbital into its a*-MO, i.e.

H 2(a-BMO) ~ M; M(d) ~ H2 (a-ABMO).
Both these operations will weaken the H-H bond (i.e. VH- H drops on complexation).
It appears that H 2 acts as a 1t-acid ligand and stability of the dihydrogen complexes (i.e. 112-H2)
depends on the metal ~ H 2 back bonding. But the limiting situation (when the metal centre is a good
donor) will lead to the dihydrido complex (i.e. oxidative addition). Thus presence of other good
~acid ligands (e.g. NO+, CO, etc.) will favour the dihydrogen complex while the presence poor
~acid ligands (e.g. PRJ) and good a-donor ligands will favour the dihydrido complex. It is illustrated
in the following examples.
• [Mo(H)2(PMe3)S] (dihydrido complex) vs. [MO(CO)3(Tl 2.H2)(Tl 2.(PR3)2] (R = isopropyl group)

(dihydrogen complex): PMe3 (in general PR3) is a better a-donor and a weaker n-acceptor com-
pared to CO. Thus replacement of PMe3 by CO (a better n-acceptor ligand) will make the metal
centre less electron donating to prevent the dihydrido complex formation. In fact, more electron
donation into the a*-MO of H 2 will tend to rupture the H-H bond to produce the dihydrido
complex [cf. H 2 ( 0'2) + 2e ~ H 22- (0'2 0'*2) i. e. 2H-].
ry
• [Re(CO)(H)2(Tl2.H2)(PMe2Ph)3]+ vs. [Re(H)4(PMe2Ph)4]+: The given carbonyl complex bears
both the dihydrogen and hydride ligands. But replacement of CO by the phosphine ligand (a
ra
better a-donor, and a weaker n-acceptor) leads to more back bonding (metal ~ a*-MO of H 2)
ib
giving rise to the more favourable condition to produce the dihydrido complex.
• The dihydrogen complexes like [Fe(CO)(Tl 2 ·H2)(NO)2], [CO(CO)2(Tl 2.H2)(NO)], etc. contain
yl
the strong n-acid ligands like CO, NO.
m
OC»\a:
am) he
lc M I
ea
H
dn
th
L (Le. H2 ) ~ M M ~ L (Le. H2 )
a-donation 1t-back bonding
e/
l -_ _--~)
~
t.m
(a)
e
dH - H = 84 pm (cf. 74.1 pm in free H2)

er
VH _ H = 2690 cm- 1 (cf. 4160 cm- 1 in free H 2)

(i.e. H - H bond elongation in the complex)
H
dw-H = 175 pm
k
lic
(b)
Fig. 10.12.11.1 (a) Metal ligand bonding interaction in M-H 2 where H 2 acts as a n-acid ligand. (b) Structural features
C
of mer i.e. trans-[W(COh(1l2-H2)(PPr3ih].
• [M II (Tl 2.H2)(H)2(PR3)3] (M = Fe, Ru) complexes bear both the hydride and dihydrogen ligands.
Here the degree of n-bonding (i.e. back donation) is controlled by the oxidation state of metal and
the existing PR 3 ligands.
(D) Examples of dihydrogen and dihydrido complexes (See Sec. 9.12): Both the examples of
H
dihydrogen (Le. 112-H2) and dihydrido (i.e. M( ) complexes are known.
H
(i) In [MO(CO)3(H2)(PPr~)2]'H 2 binds as 112-H2 in a manner similar to that of C 2H 4 to Pt in Zeise's

salt. However in solution, [MO(CO)3(H2)(PPr~)2] remains in an equilibrium mixture of MO(1l2-H 2)
/H
and Mo '\ ,i.e.
H
PPr~ PPr~
ry
OC OC
"",I/H "",I/H
OC-M~i
ra
OC-M~
I"\: H I"\: H
ib
PPri CO PPri CO
3 3
yl
m
[MO(CO)3(H2)(PPr~)2] can be prepared as follows:
[Mo(COh(PPr~)2] (16e) + H 2 ~ [Mo(CO)3(1l2-H2)(PPr~)2] (18e), (Kubas, 1980-1983~ first reported
he
the dihydrogen complex).
From [MO(CO)3(H2)(PPr~)2],H 2 can removed easily. It indicates the presence of 112-H 2 as the pre-
dominant species. lc
2- 2)(PPrj)J ;; )[ Mo(coh (OH 2)(pprj)J + H2
ea
[ MO(CO)3 (11 H
Similarly, [(lls-C sH s)Ru(1l2-H 2)(dmpe)]+ loses H 2 on refluxing in MeCN.

th
~
e/
dmpe = p p
"'" / "'"
t.m
/
Me Me Ph Ph
(iv) [TcCI(dppe)2(1l2-H 2)] can be prepared as follows:

e
er
H
k
/H
(v) In the adduct formed by Vaska's complex, Ir,\ moiety predominantly exists.
lic
H
C
(i. e. oxidative addition of H2 leading to

cis-dihydrido complex)
(vi) Dihydrogen complex may be fanned by direct ligand displacement reaction.

[CO(CO)3 (NO)] H
2
• hv ) [Cr(CO)2 (H 2 )(NO)] + CO
(vii) Dihydrogen can ligate with the coordinatively unsaturated 16e complexes (Kubas, 1980-83).
[M(CO)3(PPr~)2] + H 2 ~ [M(CO)3(l12-H2)(PPr~)2], M = Mo, W
[M(CO)3(PCY3)2] + H 2 ~ [M(CO)3(11 2-H2)(PCY3)2], M = Mo, W; Cy = Cyclohexyl
ry
Due to steric crowding (cf. cone angle of PR3, Sec. 9.10), the starting complex adopts the 16e
configuration but by accommodating the small ligand like H b it can attain the 18e configuration. This
ra
aspect has been discussed in Sec. 9.10.
(viii) Sometimes protonation of the M-H bond may produce the dihydrido or dihydrogen complex.
ib
It may lead to release hydrogen.
yl
..
H+
• /HT M/iT--. M+ + H2
m
M-H or
M"
Base H "H
he
Le., (1l2-H 2)
(a) (b)
lc
In the formation of the dihydrido (a) complex, the metal centre undergoes 2e-oxidation where H+ is
reduced to H- (i.e. oxidative addition of H+ as H-; H+ + 2e ~ H-). In the formation of the dihydrogen
ea
complex (i.e. 112-H 2) (b), oxidation state of M remains unchanged where H+ is reduced to Hand H- is
oxidised to H (i.e. H+ + H- ~ H 2). It is illustrated in the following examples.
th
[Ru(dmpe)2(H)2} MeOH , trans-[ Ru(dmpe)2 H (11

2-H 2)r + MeO-
e/
5 3)J N::, '[IrH 4(11 2-H 2 ) (PCy 3)J+

t.m
[IrH (PCy <
(E) PMR Studies to differentiate the dihydrogen and dihydrido complexes: It is illustrated for
H
e
the 112-HD and cis- M ( complexes in terms of the coupling constant J HD . This aspect has been
er
D
illustrated in detail in Sec. 12.2.19. Here it may be mentioned that use of the deuterated acid produces
the 112-HD complex. Presence of 112-HD in the complex can be evidenced from the proton NMR
H
spectrum of the complex. The PMR signal is split by coupling with deuterium (nuclear spin = I). If the
H
i.e.M( HI)
k
complex contains the moiety M ( (instead of112-HD then the PMR signal is not expected
lic
o 0
to be split to a large extent by deuterium (i.e. the coupling constant is small). In the complex, the
C
observed large coupling constant of 33.5 Hz (i.e. JHD ::::: 35.5 HZ) is comparable to that (43.3 Hz) of free
HO. It indicates the presence of 112-HD ligand.
(F) Pi-acidity of 9 2 leading to activation of 9 2 for the hydrogenation reaction: H 2 can act as a
1t-acid ligand when the metal centre is in low oxidation state and electron rich. The electron pair in the
a-bonding MO of H 2 is donated to the metal centre (i.e. a-basicity) but at the same time, electron cloud
from the filled d-orbital of the metal centre can be pushed back into the vacant anti bonding MO of H 2
through n-bonding (i.e. 1t-acidity of 9 2 ). If this n-bonding is efficient, then accumulation of electron
cloud into the a-antibonding MO will significantly weaken H-H bond. In fact, both the a-basicity (i.e.
donation of electron cloud from the bonding MO) and n-acidity (i.e. acceptance of electron cloud in the
vacant a*-MO) will weaken the H-H bond and at the limiting situation it will rupture the H-H bond
giving rise to 2H- which will be captured by the metal centre to give the dihydrido complex with the
concomitant 2e-oxidation of the metal centre (i.e. oxidative addition of H 2). Under this condition,
homolytic cleavage of H 2 will be favoured due the formation two stable M-H, i.e. metal-hydride
bonds. Thus the thermodynamic disfavour in the simple homolytic cleavage of the H-H bond is
overcome. The hydrides in the M-H bonds then can participate in the hydrogenation reactions. Such
ry
metal complexes can act as catalysts in the hydrogenation reactions.
(i) [Rh ICI(PPh3)2] + H 2 ~ [Rh III CI(H)2(PPh 3)2]
ra
(Wilkinson's catalyst)
The function of Wilkinson's catalyst has been discussed in detail in Sec. 10.13.3.
ib
(ii) 2[Co II (CN)s ]3- + H 2 --7 2[co II1 (CN)sH]3-}
yl
-CH H2 (cf· Sec. 10.6.1)
PhCH - 2 [ f-) PhCH 2CH 3
m
CO(CN)5
The mechanism of hydrogenation catalysed by [Co(CN)s]3- has been discussed in Sec. 10.6.1.
he
(iii) Vaska's complex, [Ir(CO)CI(PPh 3)2] can also activate H 2 through oxidative addition.
H
lcPh 3 P"", I/ H
ea
I
trans-[lr CO(CI)(PPh 3)2) + H 2 - / I,r' "
CI Ph P
th
CO 3
(G) Activation through the heterolytic cleavage of H-H bond: In presence of a base to abstract
e/
H+ and a metal centre which can take up H- as a ligand, heterolytic cleavage is favoured and the
thermodynamic disfavour in the heterolytic cleavage of the H-H bond is overcome.
t.m
(i) [RuCI 2(PPh 3)2] + Et3N + H2 ~ Et3N+HCI- + [RuCI(H)(PPh 3)2]

(H--acceptor) (H+-acceptor)
(ii) [RuCI 6]3- + H 2 ----7 [RuCI 5(H)]3- + H+ + CI-
(iii) . 2Cu 2+ + 3H2 ----7 2CuH + 4H+
e
(iv) AgF + H2 ----7 AgH + HF

er
10.13 CATALYSIS BY TRANSITION METAL COMPLEXES

H
10.13.1 Introduction and General Principles of Catalysis

k
Definition: A substance which can accelerate the rate of a particular reaction but not is consumed itself
lic
in the reaction is called the catalyst of the reaction. Catalysts actively participate in the reactions but
they are regenerated at some steps.
C
Energetics: A catalyst can only accelerate the rate of a thermodynamically feasible reaction. If the
reaction is not thermodynamically feasible (i.e. ~Go = +ve), then a catalyst has nothing to do with the
process. As the rates are controlled by the catalysts, the equilibrium state of a particular reaction is
rapidly attained in the presence of a catalyst.
The rate of a reaction is governed by the activation energy (Ea or ~G:t). In presence of a catalyst,
the reaction path is altered in such a way that it needs a less activation energy.
Negative catalyst: Some substances can retard the reaction rate and such substances are sometimes
referred to as the negative catalysts. In fact, negative catalysts are now known to inhibit or block some
elementary reactions of the catalytic cycle. Thus, the negative catalysts are better described by the term
catalytic poisons.
~saddle point
(a)
Uncatalysed path (single step reaction)
./ .
ry
ra
Catalysed path (single step reaction)
ib
Reactants
yl
Catalysed path (multistep reaction)
m
he
Products
-----------------------------------~~-----------
lc
ea
----+ Reaction Coordinate
th
Fig. 10.13.1.1 Energetics of an uncatalysed (a) and a catalysed (b) reaction.

Note: (a) and (b) represent the single step reaction; (c) represents a multistep catalysed reaction occurring generally in
e/
a catalytic cycle. ~G* for the uncatalysed path is always higher than ~G* for any step in the catalysed reaction.
t.m
Autocatalysts: In some cases, the catalytic agents are themselves produced in the reactions. Such
substances are called the autocatalysts. In oxidations by Mn(VII) in acidic condition, the product
Mn(II) is found to catalyse the reactions, i.e. Mn(II) appears as an autocatalyst in Mn(VII)-oxidations.
Importance in chemical industries: Most of the important synthetic chemicals (e.g. H 2S04, NH 3,
e
HN0 3 , ure~, benzene, 1, 2-dichloroethane, ethylbenzene, vinyl chloride, styrene, methanol, etc.) are
er
industrially produced through the catalytic reactions. Thus success of the chemical industries directly
depends on the principle of catalysis.
H
The available starting materials (i. e. feedstocks) for the industrial synthesis of organic chemicals are:
olefins, arenes and synthesis gas (i.e. CO + H 2). The hydrocarbons are mainly the petroleum feedstock.
k
By using these feedstocks, important organic chemicals like alcohols, aldehydes, acids and polymers
lic
are manufactured by using suitable catalytic reactions.

Biocatalysts: Most of the biochemical reactions need the biocatalysts which are referred to as the
C
enzymes. Thus the life process depends almost totally on the catalytic processes.
Homogeneous and heterogeneous catalysts: Homogeneous catalysts are in the same phase of the
reactants and products. Heterogeneous catalysts are in a different phase compared to the phase of the
reactants and products. Homogeneous catalysts generally exist as solutes in the liquid reaction mix-
tures. Heterogeneous catalysts are generally in a solid phase while the reactants and products are in a
solution phase or in a gaseous phase. In fact, for a heterogeneous catalyst, there are some active sites
on the open surface of the catalyst.
Examples of homogeneous catalysis: alkylation of benzene (Friedel- Crafts reaction), oxidation of
p-xylene to terephthalic acid, catalysis by organometallic compounds in hydrogenation, hydroformylation,
etc.
Examples of heterogeneous catalysis: Oxidation of S02 to S03 in H2S04 manufacture, ammonia

synthesis in Haber process, HN0 3 manufacture (Ostwald process) through the oxidation of NH 3 by 02;
petroleum refining, methanol production in the reaction CO + H 2, etc.
Homogeneous catalysts vs. heterogeneous catalysts: The homogeneous catalysis is generally faster
and more selective than the heterogeneous catalysis. But in the homogeneous catalysis, separation of
the product from the catalyst is a more difficult task while it is easier for the heterogeneous catalysis.
ry
Besides this, in the heterogeneous catalysis, the steric control can lead to the stereospecific reactions
(e.g. Zieglar-Natta catalyst in olefin polymerisation).
ra
Thus there are advantages and disadvantages in both the heterogeneous and homogeneous catalysts.
ib
It has been attempted to combine the advantageous properties of the both type catalysts. It has been
done by fixing the homogeneous catalysts to the surface of an inert matrix like polystyrene. Such catalysts
yl
are called immobilised homogeneous catalysts. This approach has been applie.d for Wilkinson's catalyst.
m
Examples of some important homogenous catalysis by organometallics
he
Rh
• Hydrogenation of olefins Catalyst (i.e. Wilkinson's catalyst) )
• Asymmetric hydrogenation of prochiral alkenes

lc Rh
(Modified Wilkinson's catalyst)
ea
• Hydroformylation of alkenes (oxo process)
th
e/
• Carbonylation of methanol to acetic acid.

t.m
• Olefin metathesis (i.e. olefin dismutation)

e
WOCI 4 / AICl 2 Et
2CH 2 =CHR----:....---~~ CH 2 =CH 2 + RCH=CHR.
er
@
H
• Polymerization of alkyne, 3CH==CH [Ni(acacl 2 ] ~

k
lic
Catalytic efficiency: It is measured by turnoverfrequency (N) (which is also called turnover number)
which indicates the number of substrate molecules transformed per unit time per unit molecule of the
C
catalyst when the catalyst is fully saturated with the substrate. In fact, this definition is applicable for
the homogeneous catalysts and enzymes (i.e. biocatalysts). Thus for the homogeneous catalysis, in the
conversion of R to P catalysed by C, it can be defined as follows:
R~P, rate(r) = d[P] =_ d[R]

dt dt
and, N (turnover frequency) = r/[C]
Here it is assumed that compared to the rate of the catalysed reaction, the rate of the uncatalysed
reaction is negligible.
Catalytic cycle: A catalytic process consists of a cycle of reactions that involve the catalyst, con-
sume the reactants, generate the product and regenerate the catalytic species. T~us, the catalytic cycle
goes on repeatedly.
In a catalytic cycle, several species originated from the catalyst-substrate interaction may participate.
In such cases, it is not possible to strictly define a particular speci~s as a single catalyst. In such cases,
the substance introduced as a catalyst should be better described as the catalyst precursor.
ry
Selectivity, thermodynamic and kinetic control: Sometimes, in a reaction, the reactant may be
ra
converted into different products but all are not thermodynamically equally stable. It can be illustrated
in the following reaction.
ib
yl
(Path-I)
m
(Path-II)
he
lc Saddle point
ea
th
e/
Saddle point
~
t.m
(Path-I)
Reactant
(b)
e
er
Product
H
Product
k
lic
---.~ Reaction Coordinate

C
Fig. 10.13.1.2 (a) represents the thennodynamically controlled product and (b) represents the kinetically controlled product.
Note: The (b) path may be a catalysed path. Thus the catalysed path leads to a different product from the uncatalysed
path, but it is not always true.
The product in Path-II is thermodynamically favoured (i.e. Path-II is thermodynamically controlled)

while the product in Path-I is thermodynamically less stable. By using a suitable catalyst, the reaction
may be directed to yield the epoxide predominantly and thus the product obtained is kinetically con-
trolled (not thermodynamically controlled). Thus when there are different possible reaction products, a
selective catalyst can kinetically control a particular product which is desirable (cf Fig. 10.13.1.2). In
such cases, by changing the catalysts, the products may be changed.
10.13.2 Basic Reactions Involved in the Catalysis by Organometallic Compounds

Several organometallic compounds as homogeneous catalysts find applications in many organic reac-
tions. The basic reactions involved in such catalysis are given below. It may be mentioned that for an
effective catalysis, the catalysts, i.e. organometallic compounds in the present case, must be labile.
• Coordination of ligands and dissociation of ligands.
ry
• Insertion of CO into the M-C bond and the reverse reaction, i.e. decarbonylation
• Insertion of olefin into the M-C and M-H bonds and their reverse reaction, i.e. ~-elimination.
ra
• Oxidative addition and its reverse reaction, i. e. reductive ~-elimination.
ib
• Activation of ligands through coordination and attack on the coordinated ligand.
• Activation of the C-H and H-H bond.
yl
m
Preparation of Wilkinson's Catalyst and Vaska's Compound (cf. Sec. 9.4.7F)
he
• RhCl 3 . xH 2 0 + PPh 3 (R~~~:d) >[ RhCI(PPh 3)3 ] (Wilkinson's catalyst)
(Red)
lc
Distorted square)
( planar geometry
ea
Dimerisation occurs at a relatively higher temperature.
th
• 2[ RhCI(PPh3)J;:=:=[(Ph3P)2Rh(::)Rh(PPh3)21 + 2PPh 3
e/
(orange)
t.m
• IrCl 3 .xH20+L~[Ir(CO)2 CIL]

(L=p-toluidine)
1750C
e
(R = Ph) (-L) (vacuum)

er
• Na 2[IrCI 6 ] (eth;~:~~~COI) trans -[ Ir(CO)CI(PR 3)2]

H
Vaska's complex
k
lic
10.13.3 Hydrogenation of Olefins by Wilkinson's Catalyst

It has been already mentioned (cf. Sec. 10.12.11) that the metal complexes can activate H2 either by the
C
favoured homolytic H-H bond cleavage (i.e. oxidative addition leading to the hydrido complex) or by
heterolytic H-H bond cleavage.
Hydrogenation of olefin is thermodynamically quite feasible but the process does not go on without
any suitable catalyst.
H C= CH + H ~ H C-CH , dHo = -136 kJ mol-I, dGo = -101 kJ mol- I (at room temperature)
2 2 2 3 3
To favour the process kinetically, it needs activation of both H2 and olefin. Among the different metal
complexes, Wilkinson's catalyst is quite efficient in hydrogenation of different types of alkenes at a
partial pressuse of H 2 close to 1 atm or less. The mechanism of catalysis by this catalyst has been
explored in detail by Wilkinson and coworkers and Halpern and coworkers.
A. Characteristics features of Wilkinson's catalyst

(i) Possibility of oxidative addition: The square planar complex, [RhCI(PPh3)3] i.e. chloridotris
(triphenylphosphine)rhodium(I) is a 16e-compound of tJ8 configuration and the metal centre is in a low
oxidation state. Thus the complex is an ideal one to experience the oxidative addition to attain the 18e
count and six coordination number around Rh(III).
ry
(ii) Coordinatively unsaturation and possibility to increase the coordination number: The 16e
square planar complex can attain the 18e count by simple addition of a ligand leading to a trigonal
ra
bipyramidal geometry. Here, oxidation state of Rh(I) remains unchanged.
These two properties of Wilkinson's catalyst are, in fact, common to all16e square planar complexes.
ib
(iii) Lability: The said Rh(I) complex is quite labile. This lability is an essential condition for any
yl
complex to act as a catalyst in such processes.
m
B. Steps of catalysis by Wilkinson's catalyst in hydrogenation of olefin
he
Step 1 (Ligand dissociation leading to a tricoordinate or solvated species): It is suggested that in
solution, one of the substituted phosphine ligands dissociates.
lc
[ RhCI (PPh 3)3}==' [ RhCI (PPh 3)2 ] + PPh 3, K eq -= 1.4 X10-4 mol dm-3
ea
(16e) (14e)
th
Because of the instability of 14e-complex, it has been suggested that the dissociated species remains
solvated to maintain the 16e count.
e/
L S
L", /L
t.m
Rh(I) + S "'Rh(( + L ; L = PPh 3t S = Solvent

CI/ "'-L CI/ "'- L
e
(16e) (16e)
er
(Catalyst precursor) (Active catalyst)

H
This dissociated product, i.e. [RhCI(L)2(S)] or [RhCI(L)2] is the active catalyst and the added
complex, i.e. [RhCI(L)3] may be described as a catalyst precursor complex.
k
Evidences in favour of dissociation of the substituted phosphine from the precursor complex to
lic
generate the active catalyst: The direct evidence to support this view is lacking but there are some
indirect evidences. (i) The ligand dissociation is favoured if the starting precursor complex is sterically
C
crowded (i.e. steric accleration). If the starting complex contains the less sterically hindered phosphines
(e.g. Et 3P), then the catalytic efficiency disappears. The alkyl phosphine ligand also binds more
strongly than Ph3P. (ii) If the process is started with the corresponding Ir(I)-complex, i.e. [IrCI(PPh3)3]
where the 'Ir-P' bond is much stronger than the 'Rh-P' bond, then the catalysis disappears. It again
indirectly supports that the dissociation of a phosphine ligand is essential to generate the active catalyst.
(Note: There are kinetic evidences that the starting complex without experiencing any ligand dissocia-
tion can also participate at the second step of catalysis but the rate is about 107 times slower).
Step 2 (Oxidative addition ofH2 to the active catalyst): The active catalyst generated at the 1st step
experiences an oxidative addition.
I/H
III
Oxidative addition of H2 : --~.. L-Rh--L (a cis-<tihydrido complex)
CI/I
S
ry
(16e) (18e)
ra
Note: • If the tricoordinate species [RhCI(L)2] i.e. unsolvated species is considered as the active
catalyst,· then the step can be represented as follows:
ib
H
yl
Oxidative addition of H2 : [RhCI(L)2l + H2 --~.. "'RI
L
h III- - H
m
(14e) L/ I
he
CI
(16e)
lc
• The starting complex (without the dissociation of L) can experience the oxidative addition very
slowly (ca. 107 slower)
ea
H H
I/H L I
th
L
[RhCI(L)3l + H very Slow.. -L "'Rh'-II- H
Oxidative addition of H2 :
"'L
2 ' " Rh III
L/ I
e/
(16e)
CI/ I
L CI
t.m
(18e) (16e)
Step 3 (Coordination by alkene): An alkene coordinates the cis-dihydrido complex of Rh III through
the replacement of solvent molecule. Presence of the so many good a-donor ligands like H-, CI-,
e
PPh 3 (weak n-acceptor ligand) makes the Rh(III) centre quite labile.
er
H
k
lic
C
Note: If catalysis is assumed to proceed through the unsolvated species, then this step may be represented
as follows:
Alkene to coordinate must be of appropriate size. Highly sterically crowded alkene cannot coordi-
nate and the catalysis is upset.
Step 4 (Migration of a coordinated hydride ligand to the coordinated alkene; rds): Migration of
a coordinated hydride ligand to the alkene coordinated to its cis-position generates an alkyl complex.
This reaction may be described as the migratory insertion reaction or alkene insertion into the
M-H bond to produce an alkyl complex and this step is the rate determining step.
ry
H"" /H
ra
H"" /C""
ib
c R
migratory insertion
H I
/ H
yl
(+S), (rds) 1 111
L-Rh-L
m
CI/I
S (18e)
he
(18e)
(alkyl hydrido complex)
The above alkene insertion reaction may be simply represented as:

M-H + R2C = CR 2 ~ M-eR 2-eR2H
lc
ea
The process probably passes through a four membered cyclic transition state.
th
M-H
""c I C/ -~..
e/
/ ""
t.m
The said hydrogen migratory insertion reaction is the rate determining step. It is evidenced by the
fact that for H2 the rate is much faster than that for D 2 .
e
Step 5 (Reductive elimination of alkane and regeneration of the active catalyst):

er
CH 2 R
H~I ~- .......
H
I /CH 2
,..,... CH CH 2 R
2
reductive ~
I '
L-Rh"_
1 -L
L-Rh"_I'-L + CH 3 - C H 2 R
k
c,/I elimination
c,/I
lic
(Alkane)
S H (Active Catalyst)
C
This reductive elimination occurs through a three membered cyclic transition state leading to the
transfer of the metal bound hydrogen to the C-atom of the alkyl group.
The catalytic cycle is shown in Scheme 10.13.3.1.
C. Characteristic features of the alkene

The alkene to undergo hydrogenation must not be sterically hindered to disfavour its coordination with
the metal centre. Such sterically hindered alkenes are not hydrogenated by this catalyst. If the substrate
contains more than one double bond, then the least hindered double bond is selectively reduced.
Ethylene, is not a sterically hindered alkene but it cannot be hydrogenated in this process. It is
believed that ethylene binds very strongly in the complexes and such coordinated complex cannot
further react. Moreover, ethylene as a potential1t-acid ligand and it can replace the phosphine ligand
to produce a stable complex which is catalytically inactive.
[RhCI(L)3]+C 2H 4 ~[RhCI(C2H4)(L)2J+L, K eq ;:::0.4
(L = Ph 3P)
ry
If the alkene is a cyclic one and O2 is used then it is found that cis-addition occurs exclusively.
/L
ra
L - Rh L (Precursor catalyst)
_ I-
/
CI
ib
(16e)
-s, +s,
yl
+L -L H
/8
L. c,/II /H
m
III
L-Rhl-L L - R h - L (cis-compound)
CI/ (oxidative
he
addition)
(Active Catalyst) 8
'"
(16e) (18e)
H", /H lc C=C /
'"
-C-C-
'"
ea
Reductive
/
/ elimination (coordination by alkene)
S
th
H
H\ /
e/
I-C-C-
II( \
H
/H
I
t.m
L-RH-L H-migration III
ci/l
S
(18e)
(rds)
(i.e., alkene
insertion)
S (l~L (18e)
e
(alkyl-hydrido complex) /c-c'" (l]2..alkene)

er
Scheme 10.13.3.1 Catalytic cycle in hydrogenation of alkene by Wilkinson's catalyst, [RhICI(LhJ (L = Ph3P).
H
D. Failure of Vaska's compound i.e. trans-[Ir(CO)CI(PPh 3)2] (16e, square planar complex of
£is-system) to act as a hydrogenation catalyst needs an explanation. Vaska's compound undergoes
k
oxidative addition:
lic
[Ir(CO)CI(PPh 3 )zJ + Hz ;=e [Ir(CO)CI (H)z(PPh 3 )z ]

C
In the product of Ir(III), the metal centre is inert and the neutral ligands cannot dissociate to create
a vacant coordination site to accommodate the substrate alkene. But, if the dissociation of the phos-
phine ligand can be accelerated photochemically or thermally then Vaska's compound may show the
catalytic activity.
E. Synthesis of optically active compound in enantioselective reactions by

using Wilkinson's type catalyst
In the Rh(I) complex related to the Wilkinson's catalyst, chiral phosphine ligands may be used to
generate a chiral hole in the coordination sphere of Rh so that a prochiral olefin can coordinate Rh by
using its one face preferentially. Thus, when the olefin undergoes complexation, it generates either R
or S chirality predominantly. Preferential occurrence of one such diastereomer is due to the wide
difference in lability and stability between the two possible diastereomers. This leads to enantioselectivity.
Migratory insertion of the coordinated olefin to the Rh-H bond leads to one optical isomer of the alkyl
ligand. This is the origin of stereospecificity. In some cases, the kinetic control may lead to stereospe-
cificity as in the case of L-dopa synthesis discussed below.
ry
Monsanto Company prepares L-dopa (used in the treatment of Parkinson's disease) from a substi-
tuted cinnamic acid using Rh-catalyst bearing a chiral phosphine ligand, dipamp. It is illustrated in
ra
Scheme 10.13.3.2. Thus the use of a catalytic amount of a chiral compound can produce a large amount
of an optically pure compound. In the same way, L-phenylalanine is manufactured in a large scale for
ib
the production of aspartame, an artificial sweetner. In fact, this chiral synthesis is important for the
yl
industrial production of chiral pharmaceuticals and many other chiral compounds.
m
L = may be solvent
he
lc
ea
th
e/
t.m
Two possible diastereomers

e
er
H
Substituted cinnamic acid derivative

H
2.
[Rh(dipamp)]+
0
M e 0 ) Q r X C 02 H
H
k
MeCOO . NHCOCH 3
lic
~ Hydrolysis
C
is used for
its hydrogenation to produce L-phenyl-

alanine required to manufacture
aspartame. C6HsCH2CH(NH2)C02H
(phenylalanine)
Scheme 10.13.3.2 Enantioselective synthesis of L-dopa from the substituted cinnamic acid by using Wilkinson's catalyst
bearing a chiral phosphine diligand (dipamp).
Here it is worth mentioning that between the two diastereomers, i.e. [Rh(alkene)(dipamp)HJ and s
[Rh(alkene)(dipamp)HlRwhere alkene denotes the substituted cinnamic acid undergoing hydrogenation,
the predominant diastereomer of R-configuration is kinetically less active (i.e. higher activation
energy) than the minor diastereomer of S-configuration which leads to the desired product L-dopa
or L-phenylalanine (cf Fig. 10.13.3.1).
ry
Saddle point
ra
ib
>.
~
yl
S-(Diastereomer)
a5 (Minor)
m
Q)
~
en
a
.0
he
R-(Diastereomer)
(Major)
Product
lc
ea
----. Reaction coordinate
Fig. 10.13.3.1 Illustration of kinetically controlled stereospecifity where the minor isomer reacts faster.
th
10.13.4 Hydroformylation Reaction (Oxo-Process)

e/
A. General features of the reaction

t.m
Hydroformylation reaction: In this reaction, an alkene reacts with CO and H2 to produce an aldehyde
having one more C-atom than in the starting alkene.
e
o R-CHCH 3
II
er
R-CH==== CH 2 + H2 + CO CoorRh- ... RCH CH - C - H + I

~c"" H
Catalyst 2 2
o~
H
k
Thus apparently, H 2 and CO are added across the double bond to give the aldehyde, The term
hydroformylation arises by the consideration of addition of formaldehyde (HeHO) across the
lic
double bond leading to an extension of the C-chain by one unit. The introduction of an a-atom
generates an active functional group.
C
+HCHO
But in terms of the reaction mechanism, the process is not so straight forward and the term appears
misnomer. In fact, in terms of the reaction mechanism". the process should be better described by
hydrocarbonylation process.
Markownikoff and anti-Markownikoff addition to the double bond: The products can be formally
represented as follows:
R",
H- C-CH (Markownikoff product)
R,
I I 2
CHO H (Branched chain product)

" H2 + CO
C=CH 2 ~
(H-GHO)
ry
/
H
R",
ra
""---~ H- C-CH 2 (Anti-Markownikoff product)
I I
ib
H CHO
yl
(Straight chain product)
Relative amounts of the straight and branched-chain aldehydes in the product: Relative amounts
m
of these isomeric products depend on the nature of R and catalyst. These aspects will be discussed later.
he
It may be mentioned that the straight chain product is more desirable in chemical industries.
Economic importance: The aldehydes produced are unltimately converted into alcohols which are
industrially important to manufacture the detergents and plasticisers (e.g. 2-ethyl-I-hexanol). In fact, in
lc
this process, several million tons of aldehydes are annually produced.
ea
B. Proposed mechanistic steps of the process in presence of Co-catalyst: [C0 2(CO)s] is the catalyst
precursor and the process operates under the conditions: about 200 atm pressure (i.e. fairly high pressure)
and 140-180°C temperature range in presence of a solvent. Under these conditions, finely divided Co
th
metal or any Co-salt may be used as the catalyst precursor. From these, [C0 2(CO)s] is produced.
e/
Step 1 (Generation of the active catalyst): From the catalyst precursor [C0 2(CO)s], the active
catalyst [HCO(CO)4] (an 18e species) is generated.
t.m
[C0 2 (CO)8J + H 2 ~ 2[HCO(CO)4] ; (equilibrium is attained at high pressure)

octacarbonYI) (18e)
( dicobalt (Tetracarbonylhydridocobalt)
Step 2 (Generation of the coordinatively unsaturated complex [HCO(CO)3]: [HCO(CO)4] tends

e
to decompose to release CO. To prevent this decomposition, it needs a high pressure of CO. Through
er
decomposition, it produces a 16e species [HCO(CO)3] (which is coordinatively unsaturated) that re-
mains in equilibrium with [HCO(CO)4]'
H
[HCO(CO)4J~[HCo(CO)3] + CO
k
(18e) (16e)
lic
This electron deficient species [HCO(CO)3] actually participates in the catalytic cycle. Thus, this
species may be considered as the active catalyst.
C
Note: An optimum partial pressure of CO is required for obtaining a good yield. To generate
[HCO(CO)4] and for subsequent CO coordination, partial pressure of CO should be sufficiently high.
But at very high pressure of CO, generation of the active catalyst [HCO(CO)3] from [HCO(CO)4]
through the CO-dissociation will be disfavoured to hamper the catalysis.
Step 3 (Coordination by olefin): Olefin coordinates with the coordinatively unsaturated species
[HCO(CO)3] to generate an 18e species.
HCO(CO)3]
•
[
~ (18e)
RHC---CH 2 (112-olefin)
Step 4 (Migratory insertion of the olefin into the Co-H bond): Coordinated olefin is inserted
into the Co-H bond giving rise to an alkyl complex which is a 16e species and keeps a vacant
coordination site. At this stage, two isomeric (i.e. branched and linear alkyl groups) complexes may
result. It arises so from the fact that hydride can migrate to any olefin carbon. To stabilise the resulting
alkyl complexes (16e species), CO (whose partial pressure is high) coordinates at the vacant coordinate
site to generate the 18e species.
ry
Formally it can be stated that the branched chain alkyl complex results from the Markownikoff
addition of Co-H to the coordinated alkene and the straight chain alkyl complex result from the anti-
ra
Markownikoff addition of Co-H to the coordinated alkene.
I i
ib
H H-CO(CO)3 J
~[RCH2CH2-COI(CO)3] {CH3-CH-CO (CO)3
H
yl
"'-c--L C/
I
m
R/ "'-H
(18e) (16e) (16e)
he
I
[RCH 2CH 2CO (CO)3] + co ~ [ RCH~CH2COI (CO)4]
lc (18e)
ea
R R
I co ~[ CH3CHC0 1(CO)4]
I
th
[CH 3CH -COI(CO)3 ] + (18e)

e/
Step 5 (Migratory insertion of one coordinated CO group to give the acyl complex): One coor-
dinated CO group in the alkyl complex migrates to the position between the alkyl group and Co-atom
t.m
to give the acyl complexes.

e
OC- rl(CO)3]
er
[ CH 2CH 2R
(18e)
H
k
lic
l
o c - r (CO)3 ] -~. fO '(CO)3
C
[ R-CH-CH 3 C1====o (16e)
(18e)
R-CH-CH 3
Step 6 (Oxidative addition of H 2 to the 16e acyl complex)
RCH2CH2 - C- COI(CO)3]~[RCH2CH2- C- COIII(~)2 (CO)3]

II II (cis - dihydrocomplex)
[
°
(16e)
° (18e) . _
RCH - C - COl (CO)3 ]~[RCH~. - C - CO (H)2 (CO)3]

IIl
I II I II (cis - dihydrocomplex)
[ CH 3 0 CH 3 0
(16e) (18e)
Step 7 (Reductive elimination of aldehy~e and regeneration of the active catalyst):
ry
o
RCH 2CH 2 -C-COIII(H)(CO)3]~[HCO(CO)3J + RCH 2CH 2- C (
ra
[ II I 'H
o H
ib
o
[
RCH-C-COIII(H)(CO)3]~[HCO(CO)3J + RCH-C('
yl
I II I I 'H
CH 3 0 H CH 3
m
Thus the activ,e catalyst [HCO(CO)3] (16e species) is regenerated and it can again start the reaction
he
with olefin.
Note: [HCO(CO)4] may participate in two centre reductive elimination process to give the product
and catalyst precursor, [Co 2(CO)g] as follows.
[RCH2CH2-~-CO(CO)3]
lc
co.=[RCH2CH2-~-CO(CO)4]
ea
+
(Acyl complex) (16e) (18e)

th
~O
e/
[HCO(CO)4] + [RCH2CH2-~-CO.(CO)4 ]----7RCH2CH2 -C" H + [C02(CO)a]

t.m
C. Monitoring of the product ratio, linear chain aldehyde and branched chain aldehyde: It has
been already mentioned that the linear chain aldehyde is more important industrially. The isomeric
alkyl groups are produced from the migration of hydride to t~o possible C-centres of the coordinated
e
olefin (cf Step-4). To get the higher yield of the linear chain aldehyde, it is required to prevent the
er
formation of the branched chain alkyl complex. It has been noted that if the reaction is carried out
in presence of P(n-Bu)3 i.e. PBU3' then the straight chain product predominates. It is suggested that
H
in presence of P(n-Bu)3' it competes with CO to coordinate with the Co-centre and it leads to the
formation of [HCO(CO)3PBu3]. Participation of this species in the catalysis produces the alkyl complexes
k
[RCH2CH2-CO(CO)3(PBu3)] (I); [CH3CH(R)-Co(CO)3(PBu3)] (II)

lic
Between the 18e-species I and II, because of the less steric crowding I, it is more stable than II. If
'CO' remains coordinated in place of PBU3, then the steric crowding is not so remarkable to give any
C
preference between these two species (I, and II).

K eq « 1 for L = PBu 3
Keq ~ 1 for L = CO .
In other words, we can say:
Keq(L=CO)
-~----»1
K eq (L = PBu 3)
H " ( [Co 2(CO)al ....~~_C_O_ Coo ~ CO COli

2
~ (reduction)
[HCO(CO)4] (18e)
T
ry
ra
RCH=CH [!(CO)3]
ib
2
~ [HCO(CO)3] -----~•• H2C -CHR
(Reductive (16e) (olefin coordination)
yl
elimination) (18e)
+
m
H
I (18e)
he
IIl
CH 3CH(R)-- C - CO H(CO)3 (olefin insertion
II
o lc into the
Co-H bond)
ea
J
th
H (oxidative
2 addition)
e/
t.m
I
[ RCH 2CH 2 -CO (CO)3 ]
(16e)
+
e
(16e-species)
er
(Alkyl complex)
H
k
CO
(CO insertion
lic
into the Co - C bond)

C
I
[ RCH 2CH 2 -CO (CO)4 ]
+
[ CH 3CH(R) -COl (CO)4 ]
v
(18e)
Scheme lO.13.4.1A Schematic representation of the catalytic cycle of hydroformylation reaction. It represents the cycle
leading to generation of the active catalyst [HCO(CO)3] through the oxidative addition of H 2 on the acyl complex of
Co(I) followed by the reductive elimination of aldehyde.
[ RCH2CH2-~-CO(CO)4]
+
Two c~n~re ~eductive
o
I 0
I
(18e) elimInatIon
CH3CH(R)-~-CO(CO)4]
ry
[
ra
CO~
ib
yl
m
he
(16e)
(Acyl
lc
ea
complex)
th
Scheme 10.13.4.1B Regeneration of the catalyst precursor [Co/CO)g] through the double centre reductive elimination
in hydroformylation reaction.
e/
Thus in presence of PB U3' the linear alkyl product (I) is more preferred because of less steric
t.m
crowding. The alkyl complex, [RCH 2CH 2-Co(CO)3(L)] participates in CO group insertion in the
Co-C bond as usual (ef. step 5).
D. Disadvantages in hydroformylation reactions catalysed by cobalt: (i) Though the catalyst is
commercially cheap, the process running under the conditions of high pressure (ca. 200 atm) and
e
temperature (ea. 140 -180°C) is costly. (ii) Very often, the undesired branched chain product predominates
er
over the straight chain product. However, the use of the modified catalyst [HCO(CO)3(PBu3)], can give
the straight chain product as the predominant one. But the process becomes slower and it needs a higher
H
operating temperature. (iii) About 15% of alkene is lost through hydrogenation (ef hydrogenation by
Wilkinson's catalas). (iv) [HCO(CO)4] is volatile and product is very contaminated by this. It must be
k
separated and recovered for recycling.

lic
All these disadvantages are more or less absent in the Rh-catalysed process which is discussed
below.
C
E. Use of a Rh-catalyst in hydroformylation reaction: [Rh(CO)H(PPh3)3] (trigonal bipyramidal

structure), an 18e species has been suggested as the catalyst precursor. It loses one phosphine ligand to
form the coordinatively unsaturated 16e species [Rh(CO)H(PPh3)2] as the active catalyst.
[Rh(CO)H(PPh 3)3}={ Rh(CO)H(PPh 3 )J + PPh 3

(18e), Catalyst precursor (16e), (active catalyst)
The active catalyst may be obtained as follows also:
[Rh(CO}zH(PPh 3)2];:=' [Rh(CO)H(PPh 3)2] + CO

(I8e) (16e)
This Rh-catalyst is definitely more costly than the cobalt carbonyl catalyst but it can work at a
moderate temperature and one 1 atm pressure. The probable catalytic cycle is outlined in Scheme
10.13.4.2.
In the present catalyst, presence of the bulky PPh3 ligands favours the straight chain product
rather than the branched chain product because of the steric ground.
ry
ra
ib
yl
1~
m
H +L -l H2 C=CHR H
L, I /H L, H
I
-II
he
-(A--"llk~en-e---3.~
"'- L"" CHR
/
I
" III , 1/
Rh -~----~ Rh Rh
DC
/ LI " ~O (Reductive
/ C~ elimination) DC
/ '-..
"L coordina~ion) L I CH 2
(16e)
lc CO
(18e)
(1l2-alkene)
ea
(18e) CH 2CH 2 R
Olefin insertion
th
H2 (Oxidative addition)
into the Rh-H
bond
e/
o
t.m
L
II
C-CH CH R L
CO
I CH 2 CH 2 R
"" 1/ 2 2 (CO insertion i n t o " / - L /CH 2CH 2 R
Rh the Rh - C bond) Rh "
/ '" ~ ~ " "Rh
e
OC L / "'L \ /"
OC "L
er
(16e) (18e) CO OC (16e)

(Acyl complex) (Alkyl complex)
H
k
Scheme 10.13.4.2 Catalytic cycle for hydroformylation of alkenes using triphenylphosphine complex of Rh(I) as
a catalyst.
lic
10.13.5 Monsanto Acetic Acid Synthesis

C
Acetic acid is required to synthesise many industrial products like cellulose acetate, acetate esters
mainly used as solvents, vinyl acetate, pesticides, etc.
Dilute acetic acid solutions can be prepared by bacterial aerobic oxidation of ethanol solution. But
in this process, concentrated acetic acid cannot be prepared. The commercial process (called Monsanto
process, developed by, Monsanto Company) is the Rh-catalysed carbonylation of methanol.
Rh 1-
CH 3 0H + CO (1800C, 3~-40 atm.) ) CH 3 C0 2 H
In this process, all other Gr. 9 metals i.e. Co, Ir can also catalyse but Rh catalyses the process best.
ORGANOMETALLIC REACTIONS AND THE RE~CTION PATHWAYS: REACTIVITY OF COORDINATED LIGANDS: CATALYSIS 1621
The active catalyst [Rh(CO)212]- is readily produced under the operating condition from the com-
mercially available RhCl 3 . 3H20.
RhCl 3 ·3H 20 (r~~~t:~n» [ Rh (CO)2 12 J- (16e species)

The starting material CH30H is easily obtained from synthesis gas/water gas enriched with H2
ry
content.
co + 2H 2, Zn/Cu-oxide) CH 0H
ra
3
Synthesis gas
ib
CH 30H is also readily obtained from the catalytic oxidation of methane (the main component of
yl
natural gas). If a mixture of methane and oxygen (9 :1 by volume) is passed through a heated Cu-tube
(-200°C) under a pressure of about 100 atm, methanol is produced.
m
1 Cu(200°C)
CH 4 +"2° 2 -100 atm ) CH 3 0H
he
A. Mechanistic steps of the catalytic cycle:
lc
Step 1 (rds; oxidative addition of CH3I to the active catalyst, [Rh(CO)2I2]-' a 16e species): The
ea
active catalyst is readily produced from RhCl 3 . 3H20 under the operating condition. This four coordi-
nate 16e species of Rh(l) (i. e. t!' system) is ideal to experience the oxidative addition.
th
e/
t.m
(Oxidative addition)
e
(18e, C.N. 6)
er
Step 2 (Migratory insertion of the CO group into the Rh-C bond): One of the coordinated CO
H
groups is inserted into the Rh-CH 3 bond to give an acetyl complex, a 16e species.
k
lic
COCH 3
I", I
C
CO migratory insertion i.e. Rh l_1I -CO

~
1/1
I
(18e) (16e), coordinatively unsaturated
Step 3 (Coordination of CO to the coordinatively unsaturated acetyl complex): CO group

coordinates to the vacant coordination site of the acetyl complex and restores the 18e count:
[Rh" I (CO)(COCH 3)Oh]- + CO~[ Rh lll (CO)2(COCH 3)O)3]-
(16e) (18e)
COCH 3 COCH 3 -
I I I I /CO
"'Rh l1I
_ -CO + CO ~ "'Rh"
1/1 1/1 "'co
ry
i.e.
I I
ra
(16e) (18e)
ib
Step 4 (Reductive elimination of acetyl iodide and regeneration of the active catalyst):
yl
m
COCH 3 , COCH 3
I III/CO ,': CO
1/
he
I"" I, I CO
""R~/
", I III
Rh Rh
1/ I ""co 1/1 ""co lc (Reductive

elimination)
I / ' " CO
I I
ea
(16e)
(18e) (Active catalyst)
th
Aacetyliodide on hydrolysis produces acetic acid and hydroiodic acid which can be used to generate
e/
methy1 iodide.
t.m
CH 3 -C-I
II
o
e
er
Role of 1- as a cocatalyst: 1- (i.e. iodide) is essential as a cocatalyst in this process. No other anion
including the other halides can perform the task. This uniqueness for 1- arises from the following
H
factors.
(i) [RhX 2(CO)2]- (X = CI, Br), is more reluctant to undergo oxidative addition because of higher
k
e.!ectronegativity of Cl, Br. In fact, [RhX 2(CO)2]- is a complex where CO acts as the n-acid ligands
lic
and higher electronegativity of X will destabilise this CO adduct.

(ii) Oxidative addition of CH 3I to [Rh(CO)2I2]- is the rate determing step. Among the different
C
methyl halides (CH 3-X), this oxidative addition step is kinetically most favoured for CH 3-I (cf
reactivity order: CH 3-I ) CH3-Br ) CH 3-CI ) CH 3-F.
(iii) For the soft Rh(I) centre, 1- being typically soft is an ideal ligand.
(iv) The acid strength sequence HI ) HBr ) HCl indicates that regeneration of methyl halide from
methanol is most favoured for HI.
CH 30H + HI ~ CH 3-I + H 20
In fact, this is a key reaction for the overall success of the process. For the other weaker acids like
HCl, HBr, the process is not so favoured.
ry
HI
ra
CH 31
ib
[Rh' (CO)212f ""-_;;;::a""",_ _.. [CH 3Rh"(CO)2 13]-
CH-C-I
Oxidative addition
3 II (16e) of CH 3 1, rds (18e)
yl
o
i
m
CO,I-
l
Rh"
he
lc o
ea
[(CH 3CO)Rh"' (CO)2 13 ] - ... --,,==----- [CH 3 -
II
C-
lll
Rh (CO)1 3f
(16e) (Acetyl complex)
th
(18e) '\
CO
e/
Scheme 10.13.5.1 Schematic representation of catalytic cycle for the synthesis of acetic acid though carbonylation of
methanol in Monsanto process using the rhodium catalyst.
t.m
B. Synthesis of acetic anhydride from methyl acetate:

o
e
II
er
CH-C
3 '"
CH-C-OCH + CO o
II
H
Lil
3 3
CH-C/
o 3 II
k
o
lic
The carbonylation reaction follows the same catalytic cycle described in Scheme 7.13.5.1.
C
Acetyl iodide produced through the reductive elimination of [Rh(CO)2(COCH 3 )I 3 ]- reacts with acetic
acid to produce acetic acid anhydride. The corresponding reactions are:
o 0
II II
CH 3 -C-1 + CH3-C-OH~(CH3CO)20 + HI
HI + CH 3 COOCH 3 (starting material) ~ CH 3 C0 2 H + CH 3 1

Me-I required for the oxidative addition to the catalyst is also obtained from the following reaction.
CH 3COOCH 3 + Lil ~ CH 3 COO- Li+ + CH 3 1
CH 3COO- Li+ + CH 3 COI ~ (CH 3 CObO + Lil
10.13.6 Wacker Process (Smidt Reaction): Paladium Catalysid Oxidation of Olefin

A. General features of the process
Oxygenation of hydrocarbons is an important step in the synthesis of organic chemicals. For this
purpose, the common sources of oxygen are CO (e.g. hydroformylation reaction, Monsanto acetic acid
synthesis), H 20 (e.g. HgII-catalysed hydration of acetylene), and aerial O 2 (cf. Wacker process).
ry
In Wacker process, olefins (specially ethylene) are oxidised to aldehydes by 02. The process was
developed by Smidt at Wacker Chemie in Germany in the late 1950s.
ra
PdCI 2 ' CUCI 2 /0
ib
120°C, 4 atm )CH 3 -C"
H
yl
Thus the aldehyde obtained may be us~d for the synthesis of many other organic chemicals. Here,
m
it may be noted that the hydroformylation reaction yields also aldehydes from olefins but in the product
the number of C-atom increases by one. In the Wacker process, the number of C-atom remains un-
he
changed. In this process, ethylene can be oxidised to acetic acid via acetaldehyde.
B. Steps of the Wacker process

C 2H4 is hydrated in presence of PdCl 2 i.e. [PdCI4 ]2-
lc
ea
C 2H 4 + [PdCI 4]2- + H 20 -7 CH 3CHO + Pd(O) + 2H+ + 4CI- ... (i)
th
Thus C 2H 4 is oxidised to CH 3CHO and Pd(II) is reduced to elemental Pd. If Pd(O) can be easily/
quickly brought back to Pd(II), then Pd(II) can function as a catalyst in the said hydration process.
e/
Simple aerial oxidation of Pd(O) to Pd(II) is a very slow process but it can be catalysed by Cu(II) as
CuC1 2 i.e. [CuCI4 ]2-
t.m
Pd(O)~Pd(II),(very slow)
0., 2- ( )
Pd (0) CU~12) [PdCI 4 ] very fast
e
,
er
The catalysis by Cu(II) in the oxidation of Pd(O) to Pd(II) by O 2 involves the following two reactions.
Pd(O) + 2[CuCI4 ]2- ~ [PdCI 4 ]2- + 2[CuCI 2]- ... (ii)
H
2[CuC1 2r +-.!.02 +2H+ +4Cl- ~2[CuCl4f- +H 20

k
... (iii)
2
lic
i.e. Pd(O) is oxidised to Pd(II) by Cu(II) which is reduced to Cu(I); and aerial O 2 oxidises Cu(I)
to Cu(II). The sum of the reactions (i), (ii) and (iii) gives the following net reaction and observed rate
C
law.
c. Mechanistic steps of hydration of alkene (i.e. reaction i) in Wacker process

Step I (Formation of an alkene complex): The square planar [PdCI4]2- complex experiences the ligand
displacement by C 2 H 4 to produce [Pd(C 2 H4 )CI 3]-, an analogue of the anion of Zeise's salt.
2-
CI CI
[
CI)Pd:::C1 ]
+ CI-
ry
ra
The reaction may produce the dimeric compound to some extent.
ib
yl
m
It is evident that higher CI- concentration will shift the equilibrium to the left. In fact, at much higher
he
CI- concentration, the catalysis gets hampered.
Note: [Pt(C 2H4 )CI3]- vs. [Pd(C 2H 4)CI3]-. The Pd(II)-complex can participate in the catalytic cycle but
lc
the anion of the Zeise's salt cannot. It is due to the inertness of Pt(II). In fact, Pd(ll) is more labile than
ea
Pt(II). It may be noted that on heating in water, [Pt(C 2H4)CI 3]- can release CH 3CHO as follows:
[Pt(TJ Z -C ZH 4 )Cl 3 J+HZO CH 3 CHO+Pt(O)+2H+ +3C\-

th
Heating)
Step 2 (Nucleophilic attack by H 20 on the coordinated olefin): Olefin coordinates by its

e/
1t-electron cloud and thus the coordinated olefin is relatively more electron deficient to welcome the
t.m
nucleophile. H 20 as a nucleophile attacks on the coordinated nucleophile.
"C~-
-1/c ~ ~ [CI2Pd(OH2r-CH2CH20H]
e
CI Pd
CI 3 P( l" :OH 2 -H+ [ 3 - CH 2- OC HH2] 2- __
+H_2 _O
er
'-/ ~
I -el-
(2)
H
(1 )
(~-hydroxyalkyl complex)
k
(2)
lic
Some workers have suggested that [Pd(112-C2H4)CI3]- undergoes aquation before the nucleophilic
attack, i.e.
C
2'
Note: The compound 2' can produce the product to some extent through the redox decomposition
as follows:
2- +OH
II
H3C - C - H + Pd(O) + 2CI- + H20
1----i.~. H3C-CHO + H+
ry
(2')
ra
Step 3 (f}-hydride transfer to give the Pd-H bond):
ib
u 2-
CI Pd - \ - - - - ,CH
'-~12
yl
~ ~~
3 ,
m
H ------C-H
he
OH
(3)
(1t-vinyl alcohol complex)
lc
This {3-elimination of metal alkyl complex is the reverse reaction of olefin insertion into an M-H
ea
bond.
Step 4 (Olefin insertion into the Pd-H bond to produce an isomeric hydroxy alkyl complex):
th
2-
CI2pr - \~fl H(OH)

OH
e/
, I
b
CI Pd-C-CH
I
t.m
3~ I I 3 3
H - - - - -CH 2
H
(4)
(u-hydroxyalkyl complex)
e
er
Note: 2 and 4 are the isomeric complexes.

Step 5 (f}-elimination releasing aldehyde followed by reductive elimination):
H
2-
(H'-o~
k
"'" LI (~-elimination)
lic
CI 3Pd CH -CH 3 ---~..~ CH 3CHO + PdCI 3(H)

[ ] 2-
C
(4)
I Reductive
, elimination
Pd(O) + 3CI- + H+
The elimination of acetaldehyde is also a ~-elimination process.

C. Mechanistic steps of oxidation of Pd(O) by O 2 catalysed by Cu(II) (i.e. reactions ii and iii) in
Wacker process: Oxidation of Pd(O) by Cu(II) probably occurs by an inner-sphere mechanism through
the chloride bridge. Oxidation of the chlorido-complex of Cu(I) by Oz probably involves an Oz-adduct
formation followed by generation of radicals like 02-' OH, HO z etc.
(Note: If propylene, i.e. CH3CH=CH2 is subjected to Wacker process, acetone is the final product.)
Catalytic cycle in the oxidation of ethylene to acetaldehyde by oxygen in Wacker process is shown in
Scheme 7.13.6.1.
D. Nature of the product depending on the nucleophile to attack on the coordinated olefin: In
Wacker process, ethylene is passed through an aqueous solution containing the catalyst and the nucleophile
is water (H 20). If the reaction is carried in a condition where acetate is the nucleophile, the product is
ry
vinyl acetate.
ra
PdCI 2
H2 C=CH 2 OAC - )H 2 C=CH-OAc+Pd(O)+H+ +2CI-
If the reaction is carried out in a nonaqueous solvent where CI- is the only available as a nucleophile,
ib
the product is vinyl chloride.
yl
2
CH 2 =CH 2 PdCI )H 2 C=CHCI+H+ +Pd(O)
m
he
....!.-
2
0 + 2H+
2
lc
ea
th
(2)
e/
p-elimination
Pd(O) ~----~-- Pd(CH2CH20H)CI2(OH2)]-~-------'
to give the
(2') Pd-H bond
t.m
Reductive
elimination HI l2- CI- CH~
~_L
3CI-+ H+
e
[PdCI (H)]2- .. 7ination CI 3Pd-C -CH 3 ..... CI 2Pd---11

3
I
er
f 1
Olefin insertion into CH(OH)
the Pd-H bond
CH 3CHO H H
H
(4) (3)
k
Scheme 10.13.6.1 Schematic represention of the catalytic cycle in the oxidation of ethylene of acetaldehyde by oxygen
catalysed by PdCl 2 + CuCI 2 •
lic
10.13.70Iefin Metathesis Catalysed by SchrockType Carbene (i.e. Alkylidene)

C
Complexes and Alkyne Metathesis Catalysed by Metal Carbyne Complexes

The olefin metathesis reaction involves the exchange of two alkylidene groups as illustrated below.
H2C===CHR CHR
+
H2C===CHR
;-
II
CHR
2CH 3 - C=CH 2(propylene) ~ H2C=CH 2+ H3 C - CH=CH -CH 3 (butene)
The forward reaction may be considered as a dismutation or disproportionation reaction.

FUNDAMENTAL CONCEPTS OF INORGANIC CHEMISTRY
Mechanism called 'Chauvin mechanism' to honour the scientist of the reaction

catalysed by Schrock type carbene complex:
/a c'" /e
LnM=C", + C=C
b d/ "'I
ry
(starting carbene
complex)
ra
ib
yl
m
he
(c-e bond Cleavage)! (Metallacyclobutane
b transition state)
a~/
C
lc
/e
ea
LnM===C",
Ln-1 M /\ C-c
f
\1
th
(New Carbene
Complex)
/:C~
e/
e f
• •
t.m
(Olefinic complex)
e
The new carbene cOmpleX,LnM=C( can act as the chain carrier as it can again participate in
. f
e
forming the metallacyclobutane interme~late. For an effective catalysis, presence of the ligands (L)
er
containing the =0 and -OR moieties (to~act as the n-donor ligands) and high oxidation state of the
metal centre in the starting carbene compleJx are required. The n-donor property of the =0 and -OR
H
ligands towards the metal centre (with higH oxidation state) can stabilise both the starting complex and
metallacyclobutane transition state. Schr~k catalyst (Mo-carbene) and Grubbs catalyst (Ru-carbene)
k
are widely used in olefin metathesis.

lic
Here it is worth mentioning that the metal carbyne complexes can catalyse the alkyne metathesis
in the same way through the formation of metallacyclobutadiene type transition state.
C
V
Metallacyclobutadiene
10.13.8 Ziegler Catalyst and Ziegler-Natta Catatyst: Polymerisation of Olefins

A. General features of polymer and polymerisation-Stereoregular and stereoirregular
polymers .
There are two types of polymer: addition polymer (e.g. poly-olefins) and condensation polymer (e.g.
nylon).
ry
Stereoregularity of polymers: Stereochemical configuratipns of the repeating monomeric units main-
tain a certain order in a stereoregular polymer. It is illustrated f~r the polymer polypropylene obtained
ra
from propylene.
'" '" '" ""

H3C H H3C H H3C H H3C H
ib
/ / / /
"'" /c~ /c~ /c"'" /c"'" /
yl
(Isotactic - all chain C-atoms
bear the same configuration)
m
/c~ /c'" /c"" /c"" /c~
he
H H H H H H H HH H
(Stereoregular polymer)
lc
ea
(Syndiotactic - alternate C-atoms
th
bear the same configuration)

e/
t.m
(Stereoregular polymer)
e
(Atactic - no regularity of
er
configuration of the C-atoms)

H
k
(Stereoirregular polymer)
lic
Fig. 10.13.8.1 Stereochemical aspects of the linear polymer-polypropylene.
Here it may be mentioned that nature has prepared many stereoregular polymers like-quartz, cel-
C
lulose, DNA, RNA, etc.

Stereoregular polymers possess the properties like: higher strength, higher melting point, easy to
crystallise, etc. But these properties are lacking in stereoirregular polymers where the stereochemical
configurations of the repeating monomer~~ are different.
Process of polymerisation: The important pathways are: free radical initiation, ionic mechanisln
(which may be acid catalysed or base catalysed) involving the carbonium or carbanion centres, initia-
tion by organometallics (e.g. RLi, R 3AI, R 3AI + transition metal salts as cocataysts). Very often,
stereoregular polymers are obtained by using the organometallic initiator (e.g. polymerisation of olefins
by Ziegler-Natta catalyst).
B. Ziegler catalyst and Ziegler-Natta catalyst: K. Zeigler (Germany) established (in 1955) the
process of organoaluminium catalysed polymerisation of olefins (e.g. ethylene, propylene). The process
was further developed by G. Natta (Italy) by using aluminum alkyl along with other transition metal
compounds, typically TiCl 4 (i.e. the mixed catalyst was developed by G. Natta). For this contribution,
they were jointly award the Chemistry Nobel Prize in 1963. In fact, this contribution is of tremendous
industrial importance.
ry
Ziegler catalyst: Aluminium alkyls i.e. AIR 3 or Al 2R6
Ziegler-Natta Catalyst: AIR3 + TiCl 4 or AIR 3 + TiCl 3
ra
If VCl 4 is added in place of the Ti-salt, the mixture is also active.
C. Application and function of Ziegler catalyst: Ziegler catalyst was applied for the following
ib
purposes.
yl
(i) Synthesis of long-chain (C 14 - C 20 ) unbranched alcohols which are important in the manufacture
of biodegradable detergens (i.e. R-CH 2-O-S0 3- Na+, R = C II to CIS)
m
(ii) Manufacture of isoprene required for the manufacture of rubber.
(iii) Manufacture of soft polythenes.
he
Mechanistic steps of olefin polymerisation in presence of Ziegler catalyst: It goes on through the
insertion of alkene into the 'AI-C' bonds of monomeric AIR 3 .
/
lc
(C2H4 )x - C2Hs
ea
100-140°C
• AI - (C2 H4 )y - C2 Hs , x + y + z =3n
100atm
""
th
(C2H4)z- C2 Hs
e/
The value of x, y and z can be controlled by monitoring the temperature, pressure and time. It is
believed that C 2H4 makes a 112-coordination with the coordinatively unsaturated AI-centre followed by
t.m
the rate determining migration of an alkyl group fronl Al to the olefinic C-atom (effectively the process
leads to insertion of C 2H4 into the AI-R bond).
e
CH 2
'" '" AI' "0'\CH

er
AI-CH -CH (Metallocyclobutane)

2
/ 2 3 (ethane) '~,'
/ , ,
H
'CH 2 -CH 3
j Slow
k
(Migratory insertion)
lic
~
------- "'AI-(C H) - E t
'"
/AI-(CH 2 CH 2) - E t
C
/ 2 42
Synthesis of straight chain alcohols (C 14 to C 20): By monitoring the external condition, degree of
polymerisation may be controlled to make x, y and z around 6. Then the required straight chain alcohols
may be obtained as follows:
(a) /"AI(C2H4)6-C2Hs (i) ?xidation(?2) ) "AI(OH) + HO(C H ) -Et
(II) HydrolysIs / 2 4 6
The controlled oxidation by O 2 produces aluminium alkoxide (i.e. )AI- OR) which on hydrolysis
gives the final product.
AI + CH2-Rh --~~°2
.. AI +O-CH 2- Rh
~ Hydrolysis
AI(OHh + 3RCH 2-QH
ry
(b) Alternatively, on thermal pyrolysis, ~-elimination releases an alkene (cf. ~-elimination of alkene
ra
is the reverse process of olefin insertion into the M-H bond)
ib
""- AI- - - - - - CH 2
yl
/ :I :1
I (f3-elimination) ""-
I I
• / AI-H + RCH===CH 2
m
I I
H------C-R
he
H
Metallacyclobutane
RCH=CH 2 can be used to manufacture the straight chain alcohols.

lc
ea
Manufacture of polythene: The degree of polymerisation of ethylene by using the AI(Et)3 catalyst
may be controlled giving rise to the C-chain length up to C 200 • It gives a soft polyethene polymer
(melting point -1 aaOC).
th
Synthesis of isoprene from propene (CH3 -CH = CH2): If propene or higher alkenes are used,
e/
then only a single insertion occurs into the AI-C bonds. It leads to dimerisation of propene to
2-methylpentene-l which on pyrolysis gives isoprene for the use in the industrial production of rubber
t.m
(i.e. cis-I, 4-polyisoprene; cis-form =:::) natural rubber, trans-form =:::) gutta percha).
CH 3
I
e
""- CH 3CH=CH 2 ""-

AI - CH 2CH 2 - CH 3 ~ AI - CH 2- CH - CH 2CH 2CH 3
er
(olefin insertion into /

/
i.e. AI(n-Pr)3 the AI-G bond) J
H
f3 -elimination
""- RCH=CH 2
~
""-
k
AI - H AI - CH2CH 2 R ""- /CH 2CH 2CH 3

H + H C=C
lic
/ / AI -
(R = CH 3) / 2 ""-
CH 3
C
(2-methylpentene-1 )
H
I
H2C=C-C=CH
I 2
CH 3
(isoprene)
(RLi) ~ Polymerisation
Isoprene
(RLi) ~ Polimerisation
H H
'/
H
,/" /
H H CH 3 H
ry
i.e. /~ /c'" /c=c'" /
/C-C /,C C
ra
-, /,
H3 C H H H H H
ib
(natural rubber)
(cis-1, 4-polyisoprene)
yl
Note: Alkyllithium (RLi) is widely used as an initiator for olefin polymerisation. The process passes
m
probably through the I, 2-addition of R-Li to a C = C bond.
he
lc " .".
/ ..
C=-=.-=-:C ,/'
,,'
,,' ..
-c----u
ea
/
(1l2-coordination) Cyclic Transition state
th
Thus the polymer obtained is very often stereoregular. The process passes through the cyclic tran-
e/
sition state in which the monomer will be arranged in such a way to give the minimum steric crowding.
This steric control gives the stereoregular polymer.
t.m
D_ Application of Ziegler-Natta catalyst and its function: This mixed catalyst is prepared by
mixing TiCl4 with Al 2Et6 taken in a hydrocarbon solvent. It gives a brown mixture which can polymerise
ethene (i.e. ethylene) even at room temperature and atmospheric pressure. Thus, this mixed catalyst is
e
""'-
more efficient than the single catalyst, i.e. Ziegler catalyst. c;
er
In industry, polymerisation of ethene by using this mixed catalyst is carried out at 10 atm pressure
and 50-150°C temperature. It produces the high density polyethene (characterised by no branching)
H
with higher stiffness and higher softening temperature (140-150°C). Such high density polyethenes are
of enormous utility in our daily life.
k
C 2H 4 (i) Z-N-catalyst h-Igh d ensl-ty po Iye th ene (HOP)

lic
50-1500C, 10 atm )
(ii) ~-elimination of metal hydride or hydrolysis.

C
The catalyst is to be removed to get the polymer. This can be done either by ~-elimination of metal
hydride or by hydrolysis.
Polymerisation of propene in this process produces stereoregular polypropene.
n CH 3 CH = CH 2 Z-N process
) P 0 Iypropene (stereoregu Iar )
Mechanistic steps of olefin polymerisation in Zieglar-Natta (Z - N) process: It is suggested that

AIEt3 i.e. AI 2(Et)6 reduces TiCl4 to TiCl 3 which is alkylated partially by AIEt3 . In fact, preformed TiCl 3
may be used in place of TiCl4 to get the same result. It may be mentioned that Ti(III) (d l ) is highly labile
and this lability is an essential condition for the catalysis.
C1
/
AIE~ AIE~ I/ III
TiCI 4 ---~...
~
[Reduction
of Ti(IV)]
TiCI 3 ---~~~
[Alkylation
of Ti(III)]
I
--CI-Ti-CH-CH
2 3
CI
ry
I
ra
(1 )
1 is an organometallic compound of Ti(lll) in which there are some vacant coordination sites. Other
ib
the coordinating sites are occupied by the CI- ions which can bind other Ti-centres as the bridging ligands.
Here it should be mentioned that the active catalyst Ti(III)-Et having some vacant coordination
yl
sites is remaining bound on the surface of the catalyst. Thus it is an example of heterogeneous catalyst.
m
The Ti-centres present on the catalyst surface are partially alkylated to generate the active catalyst centres.
,,2-
The mechanism involves the attachment of olefin (e.g. ethene) at the vacant coordination site
he
of the Ti-centre on the surface of the catalyst. Then it experiences the migratory insertion of the
olefin into the Ti-Et bond. This migratory insertion generates the vacant coordination site for coordi-
lc
nation by another olefin molecule which is subsequently inse~ed into the Ti-C (alkyl group) bond
leading to the C-chain elongation. The process is repeated. This is illustrated in Scheme 10.13.8.1.
ea
th
CH 3
e/
Catalyst I /1 / /l
surface cr 1/ CH 2 1/
-bti~J~ -bti~J
t.m
CI CI CI CI
e
IVI IV'
er
H
k
lic
C
Metallacyclobutane
Scheme 10.13.8.1 Schematic representation of polymerisation of ethylene on the heterogeneous catalyst surface of the
Ziegler-Natta mixed catalyst. (Transfer of alkyl group tp the coordinated ethylene involves cis-insertion).
To separate the polymeric substance from the Ti-centre, the polymerisation process is terminated by
the reverse insertion reaction, i. e. ~-elimination leading to metal hydride.
1/(1
-
-Ti-CH
/ t I
~~
2
H-C-H
ry
I~
R
ra
ib
The process can also be terminated by hydrolysis.
yl
High density (i.e. linear) polyethene (HDP): In presence of Ziegler-Natta catalyst, polymerisation
m
of ethene exclusively gives the high density polyethene characterised by straight C-chain without any
he
branching. The polymerisation process occurs on the catalyst surface of the heterogeneous catalyst. On
the surface, the required four membered cyclic transition state for olefin insertion into the Ti-C bond
is developed. The surface puts a steric control and at each step of monomer addition, the monomer
lc
adds in the same fashion. It generates the straight chain polymer. This steric control leading to
ea
stereospecific polymerisation has been discussed below.
Here it may be mentioned that the low density polyethene (LDP) (i.e. branched polyethene) is
th
commercially produced by polymerisation of ethene initiated by organic peroxide. The process goes
through the free-radical mechanism.
e/
Stereoselective polymerisation and steric control to produce the stereoregular polymer: To

understand this, we may consider the polymeric structure of u-TiCl 3 . Two-third of the octahedral holes
t.m
produced by the hexagonal close-packed (hcp) array of CI- ions are occupied by Ti in the u-TiCl 3
structure. Internal Ti-centres are octahedrally surrounded by the bridging chloride ligands but the Ti(III)
centres lying at the surface possess some vacant coordination sites. Such Ti-centres are alkylated to
e
produce the catalytically active centres.

er
When an asymmetric olefin like propene is polymerised, the cyclic transition state is produced on the
catalyst surface for olefin insertion into the Ti-C bond in a way, so that the steric hindrance will be
H
minimum. The catalyst surface will protrude the Me-group of propene (say) in the same way at each
step of cyclic transition state. In other words, orientation of the attacking olefin at each step is
k
stereoselective and the transfer of alkyl group (i.e. growing polymer chain) to the coordinated olefin
lic
will occur with the same stereochemistry. Thus each monomer will add in the same way to the
growing polymeric chain. It is evident that the setereoselective polymerisation occurs due to the
C
steric control governed by the catalyst surface. This view is supported by the fact that the fresh
homogeneous catalyst mixture of [Ti(Cp)2CI2] and [AlEt2CI] is more effective than the Ziegler-Natta
heterogeneous catalyst in polymerisation of olefins but this homogeneous catalyst mixture is not useful
in preparing the stereoregular polymers. It is due to the fact that in the homogeneous catalyst, there is
no catalyst surface to introduce the said steric control needed for the stereospecific polymerisation of
the asymmetric olefins.
Homogeneous Ziegler-Natta catalyst obtained from the mixture of [Ti(Cp)2CI(Et)] and [EtAICI 2] in
toluene probably involves the active species, [EtCIAICI2Ti(Cp)2Et] which is structurally very much
similar to the heterogenous catatyst.
(Active species in homogeneous Ziegler-Natta Catalyst)
ry
ra
10.13.9 Metal Catalysed Cyclooligomerisation of Acetylenes
Ni(II)-complex having the chelating ligands (e.g. acac-) that can be temporarily partially dislodged to
ib
accommodate acetylene in the coordination sphere act as the catalyst.
yl
H
L I
m
( H.......... C~------c
L~17:!~
he
4HC:=CH H
(-28) ..
lc
/Ni')<'''''!-I - - - . CaH a
./~c
ea
(Cyclooctatetraene)
/
(LH.. . .<~ _---J~I

+ N~(II)-catalyst
th
(Capable to provide
4 coordination sites)
(L - L = acac-) C"H
e/
H
t.m
e
( L"1,./L)
er
----.. CsH s (benzene)

H
L/I"L Ni(lI)
PR 3 - catalyst
k
(Capable to provide
lic
3 coordination sites)
C
~ No reaction
(Capable to provide
two trans-eoordination sites)
10.13.10 Catalysis in Preparation of Synthesis Gas and Water Gas Shift Reaction (WGSR)
Synthesis gas, an important feedstock: The mixture of H 2 and CO is called synthesis gas as it can be
applied in the synthesis of many industrial products-both organic and inorganic (e.g. NH 3 in Haber
process). In organic industrial chemistry, the use of acetylene and alkene (e.g. ethene, propene, etc.) as
the important feedstocks is well known. These feedstocks are chemically highly reactive also. Now,
attention goes on for the production of synthesis gas which can be generated from coal.
ry
C (red-hot coke) + H 20 (steam) ~ CO + H 2; ~H = +130 kJ mol- 1 (Endothermic); ~S = +ve
ra
This endothermic reaction can be made entropy-driven to the right at high temperature
( )1000°C). In fact, to maintain the required temperature, the following exothermic reactions are
ib
carried out periodically.
yl
2C + O 2 ~ 2CO; C + 02 ~ CO 2 (~HO = -395 kJ mol-I)
m
When CO 2 is vented away, steam is passed over the hot coke bed to allow the endothermic water
gas reaction. These e~othermic and endothermic reactions are periodically carried out. Classically, the
he
mixture of CO and H 2 obtained from the above reaction is called water gas which can be used a fuel.
But CO is tremendously toxic and consequently, leakage of water gas may cause a danger. If the water
lc
gas is made enriched with H 2 (an important fuel gas but nontoxic) at the cost of CO, then the danger
of toxicity is minimised. It is done in water gas shift reaction (WGSR). This H 2-enriched water gas
ea
is called synthesis gas which is also ind\lstrially important.
Water gas shift reaction: The ratio of CO tnd H 2 in water gas can be changed through the water
th
gas shift reaction (WGSR).

CO + H 20 (strean) -7 CO 2 + H b ~H = -42 kJ mol- 1 (Exothermic); ~S ~ 0
e/
Though the process is thermodynamically favoured in terms of enthalpy, the process is kinetically
sluggish. Th~ process can be catalysed by both homogeneous and heterogeneous catalysts.
t.m
Heterogeneous catalysts: (ZnO + Cr203); Fe304; Fe203 - Cr203. These are industrially used.
Homogeneous catalysts: Metal carbonyls like [HFe(CO)4]-, [Rh(CO)2I2]- in basi¢ solution in metha-
nol, tetrahydrofuran, etc.
e
By using the WGSR, H 2/CO ratio can be increased from unity (present in water gas). Such H 2-
enriched gas mixture is commonly called synthesis gas which can be used in many important processes.
er
Application of synthesis gas:

H
(1.) CO + 3H 2 Ni-Catalyst
6500C)
CH 4 + H 2 0 ;
( meth · process ) .
anatIon
k
This produces the synthetic natural gas (SNG) (see Sec. 10.13.12 for probable mechanism of the
lic
reaction).
synthetic petrol.
C
(ii) Synthesis gas Fischer-Tropsch process)

Fe-catalyst
i.e. nCO + (2n + 1)H 2 ~Cl1H2f1+2 + nH 2 0
(1·1·1') CO + 2H 2 Cu/Zn
50 atm, 250°C
) CH OH
3
CH 30H can be used in fuel cells and it can be blended with gasoline to prepare the fuel gasohol.
Methanol can be converted into gasoline (i.e. called synthetic petrol) by using ZSM-5 catalyst.
n CH30H~-(CH2)11 -+n H 20
Synthetic petrol
Mechanism of Water Gas Shift Reaction: The mechanism of the reaction is believed to pass
through the formation of metal-carbonyl in which the coordinated carbonyl group experiences the
nucleophilic attack by -OH or H20.
~ b+
M + :c..-o:~
ry
ra
~~ ~
ib
co ,. ~ M c===o -C02
(i) M----..M-C===O OH ~ M-C===O ~;---c.1 -~~~ M-H
~ I ~-elimination b+ :~I
yl
OH H-- ·0 Metal hydride
m
(charges not shown)
-H+
he
(ii) M-H+H+ ~M+H2 lc
or
ea
M-H+H20~M+OH- +H 2
. Common mechanistic steps of catalysis in WGSR

th
The above mechanism is supported by the fact that [HFe(CO)4]- is known to catalyse the WGSR in
alkaline solution and the reaction, occurs as follows.
e/
[HFe(CO)4]- +CO~[Fe(CO)5]+H-; H-+H20~H2+0H-

t.m
i.e. [HFe(CO)4]- +CO+H20~[Fe(CO)5]+H2+OH-

e
/OH]
!
er
Nucleophilic [
-OH + [Fe(CO)s] ------i~~ (OC)4Fe- C [Fe(CO)s]
~
H
attack of OH-
~~the coordinated ° OH
k
lic
T
C
[(OC)4FeH]-+ CO 2
~-elimination
....
41-------
:H
(OC)4Fe-C~
[(OC)4 FeH)- [(OC)4Fe(C02 H))-
~O CO 2
[RU3(CO)12] has been found to catalyse the WGSR reaction in a basic condition. The catalytic cycle
runs as follows:
ry
ra
10.13.11 Synthetic Gasoline by Using ZSM-5 Catalyst (Mobil Process)
ib
The synthetic zeolite ZSM-5 (developed, in the laboratory of Mobil Oil) is an aluminosilicate having a
yl
higher silica content and a much lower aluminium content compared to the other zeolites. ZSM-5 has
m
got some unique structural features:
(i) intermediate pore size between the smallest and largest pore size known in different types of
he
zeolites;
(ii) inter-connecting channels.
lc
All the aluminosilicates can act as the acid catalysts. In fact, replacement of Si 4+ by A1 3+ causes an
imbalance of charge and to balance the charge it needs H+. This H+ ion protonates the free OH group
ea
coordinated to AI(III). This is why, in aluminosilicates, AI-centres are strongly acidic. In fact,
aluminosilicates may be strongly acidic like concentrated H 2S04 •
th
H~ /H
e/
HO 0 + OH
I I I
t.m
--Si-O-AI-O-Si-O--
I
000
I I
I I I
e
--Si-O-Si-O-Si-O--
er
I I I
H
(Source of proton in "aluminosilicates)

k
Acid Catalysis by ZSM-5

lic
Alkylation of benzene by olefin:

C
H+ (lSM-5)
CH 2 ====CH 2 ~ CH 3 -CH 2+ (electrophile)
Isomerisation of xylene:
Me Me Me
Gt
I ~
~
c;
H+ (ZSM-5)
-H+
==m
H
-H+
ry
Me Me
H Me
ra
The rod-shaped p-xylene fits better in the cavity of ZSM-5 than the 0- and m-isomer.
ib
Methanol can be prepared from synthesis gas and methanol can converted into gasoline by using
ZSM-5 catalyst. New Zealand Government had constructed a plant in 1986 to produce the synthetic
yl
gasoline, about 627,000 tons per year.
m
nCH 3 0H ZSM-5) (CH 2)n - + nH 2 0
he
The actual mechanism is not known. The probable mechanistic steps are discussed here. ZSM-5 acts
as an acid catalyst for dehydration of methanol to produce carbene (i.e. CH 30H ~ H20 + CH 2) which
lc
is stabilised by the zeolite. At the next step, carbene is inserted into the C-H bond of another
molecule of methanol.
ea
CH2
th
i.e. HO-CH2-H~HO-CH2~H2-H
lCH,
e/
~ HO-CH 2-CH 2-CH 2 --H

t.m
The pore size of ZSM-5 can accommodate the growing straight C-chain upto C 10- Thus the
carbon chain growth stops at C 10'
H3 e-( CH 2)7-CH 2-CH 2-OH
-H20
)H 3
e-(CH
2)7-CH=CH 2
e
er
Thus the resulting hydrocarbon produces the synthetic gasoline having very high octane rating
ranging from 90-100. The efficiency of the process is very high. About 90% of the methanol is con-
H
verted into gasoline in a single pass.
10.13.12 Synthetic Gasoline by Fischer-Tropsch Process

k
lic
It is the oldest process to convert synthesis gas into gasoline. The reaction uses various transition metals
as catalysts.
C
~
CO + (2 n + 1) H 2, catalyst) C n H 2 n+ 2 + n H 2 0
Synthesis gas
Along with the saturated hydrocarbons, some alkenes and alcohols are also produced. The mecha-
nism of reduction of CO by H 2 is not well understood. But the following carbide-carbene mechanism
may be operating.
Carbide-carbene mechanism: It is believed that, CO is dissociated on the catalyst surface to
produce the metal carbide and metal oxide. Metal carbides are then reduced to carbenes which are
stabilised by the catalyst surface. On the catalyst surface, H 2 is dissociated to produce the metal-
hydrides (i.e. M-H linkages). Then surface carbenes are inserted into the M-H bonds to increase
the C-chain length.
c 0
77m711/7IIlI/777mm
co
~ ~
ry
H H
ra
H2
~
ib
Step 1: Dissociation of CO and H 2 .on the heterogeneous catalyst surface to give 'M-C' (carbide),
yl
M-O (oxide), M-H (hydride) linkages.
m
H ceo 0
he
lc
Step 2: Formation of carbene on the catalyst surface from the M-C bonds and elimination of H 20
from the M-O bonds.
ea
H CH 2 CH 2 CH 2 CH 3 CH 2 CH 2
711~ ----.. J17/Mmlldm

th
e/
Step 3: Insertion of surface carbenes into the M-H bonds to give the growing C-chain.
The above mentioned steps are given just to understand the carbide-carbene mechanism.
t.m
There are some arguments to support the carbide-carbene mechanism. It is expected that the catalyst
which will favour the decomposition of co to give the metal-carbides will be most effective.
• Platinum metals (i.e. Ru, Rh, Pd; Os, Ir, Pt) are reluctant to form the carbides and they can absorb
e
CO without much dissociation of CO. Thus, the platinum metals are not expected to act as the good
catalysts in Fischer-Tropsch process.
er
• Iron and nickel can dissociate CO at 300-420 K and form the unstable carbides and in fact these
are the good catalysts in Fischer-Tropsch process.
H
• Between Fe and Ni, the iron surface can more favourably dissociate CO to produce the carbides.
This is why, on the Fe-surface, concentration of the carbene groups is much higher than that on the
k
Ni-surface. Thus for producing the long-chain hydrocarbons, the Fe-surface is a better choice as a
lic
catalyst. On the other hand, Ni-surface which generates the less number of surface-CH 2 groups is more
suitable for producing the lower hydrocarbons like CH 4 . In fact, for methanation of synthesis gas to
C
produce the Synthetic Natural Gas (SNG), Ni is the selected catalyst.
Synthetic Gasoline vs. SNG: Fe vs. Ni as a catalyst

Thus to produce the synthetic gasoline (having C-chains in the range C IO - C l2 ) in Fischer-Tropsch
process, iron is a better catalyst while to produce SNG, nickel is a better a catalyst.
• Cobalt (Co) surface also favoures the dissociation of CO and carbene formation through the
cobalt-carbide bonds. In fact, just like iron, cobalt is also a promising catalyst in Fischer- Tropsch
process to produce the higher hydrocarbons (i.e. liquid fuel like gasoline).
• Thngsten (W) and molybdenum (Mo) are the poor catalysts in Fischer-Tropsch process. In fact,
they can dissociate CO at much lower temperature (ca. 170 K) but they form very stable carbides which
cannot be easily reduced to carbene. Thus, the carbide-carbene mechanism can explain the poor cataly-
sis by Wand Mo.
Synthetic gasoline by Fischer-Tropsch Process and Mobil Process
ry
These processes are practised where crude petroleum is costly but coal is abundant. From coal,
ra
synthesis gas is manufactured. These are mainly practised in New Zealand and South Africa where
coal is very cheap. However, in near future, shortage of crude oil may divert the attention in this
ib
direction globally.
yl
10.13.13 Catalytic Deuteration of Benzene
m
If deuterium gas (D 2) is passed through a benzene solution containing [(lls-Cp)2TaH3] then C 60 6 is
he
produced at an elevated temperature.
H D
H H
°~
2,
lc 0 0
ea
~
[(1l2-Cp)2TaH 3]
H H 0 0
th
H 0
e/
Perdeuterobenzene (C 6D6 ) is widely used as an NMR solvent. The steps leading to the catalytic
deuteration of benzene is shown in Scheme 10.13.13.1.
t.m
e
er
H
o
(5)-@-0 /~
(115-Cp)2Ta-D / 7 (1]5-CP)2Ta~ 7 (1]5_CP)2Ta ---@
k
(16e) 0
(16e)
lic
(18e)
Steps (1), (3) and (5): Reductive elimination;

C
Steps (2), and (4): Oxidative addition.

Repetition of the steps (2) to (5) in presence of excess O 2converts C 6HsD to C60 6 with the regeneration
of the catalytic species, (lls-Cp)2TaO at each cycle, i.e.
@-D excess 02
Scheme 10.13.13.1 Different reaction steps leading to the catalytic deuteration of benzene.
10.14 PHOTOCHEMICAL REACTIONS: PHOTOCATALYST (Ti0 2 )

These aspe~ts has been discussed in Sec. 6.9 and Chapter 16, Vol. 3 in detail.
EXERCISE 10
ry
1. Discuss the important factors controlling the reaction rate of CO substitution in metal carbonyls.
2. How can you prepare Fischer carbene and Schrock carbene complexes? Discuss their reactivities
ra
in terms of their structural features.
3. Metal carbonylates can act as the Bronsted bases and nucleophiles-illustrate and explain.
ib
4. Illustrate: insertion and deinsertion reaction; carbonylation and decarbonylation reaction; oxidative
yl
addition and reductive elimination; CO-scrambling reaction.
5. Critically analyse the different possible pathways of carbonyl insertion into the 'M-C' bond and
m
its reverse reaction.
6. Discuss the mechanism of: olefin insertion into the M-X (X = H or C) bond; ~-elimination;
he
a-H abstraction in elimination reaction; S02 insertion into the M-C bond; oxidative addition;
reductive elimination.
7. Discuss the possibilities of C-H bond activation.
lc
ea
8. Illustrate agostic interaction. How does it differ from the oxidative addition of C-H bond?
9. Discuss the mechanism of scrambling of Me-groups in A12Me6.
th
10. What do you mean by fluxional isomerism? How is it rel~ated with the stereochemical nonrigidity?
11. Discuss the different types of fluxionality found in the organometallic compounds. Discuss the
e/
involved mechanistic pathways.

12. Discuss the mechanism of CO-scrambling in di- and polynuclear carbonyls.
t.m
13. Discuss the reactivity cyclopentadieny I rings present in ferrocene.

14. Discuss the factors controlling the possibility of nucleophilic and electrophilic attack on the
coordinated ligands.
e
15. Discuss the possibility of nucleophilic attack on the unsaturated hydrocarbons including benzene
er
through metal coordination.

16. Discuss the phenomenon - ligand protonation.
H
17. Dioxygen (0 2) is generally inert as an oxidant. How can it be activated through complexation?
18. How is it possible to activate H 2 by using the metal complexes? Discuss the factors favouring the
k
homolytic and heterolytic fission of the H-H bond. Discuss the factors favouring the dihydrogen
lic
(1l2-H 2) and dihydrido complexes.

19. "Coordinated N 2 is more active than free N 2" - illustrate with explanation.
C
20. "Coordinated O 2 is more reactive than free O 2''- illustrate with explanation.
21. Explain the origin of catalysis and catalyst poisoning. What do you mean by turn-over number
in expressing the efficiency of a catalyst? What do you mean by thermodynamically and kinetically
controlled reaction? Comare the advantage and disadvantage in homogeneous and heterogeneous
catalysis.
22. Discuss the mechanistic steps in the following catalysed reactions:
(i) hydrogenation of olefins by Wilkinson's catalyst and its application in the production of opti-
cally pure L-dopa and L-phenylalanine; (ii) hydroformylation reaction (i.e. oxo process); (iii)
Monsanto process of acetic acid synthesis; (iv) oxidation of olefins in Wacker process. (v) olefin
.
metathesis reaction; (vi) polymerisation of olefin by Ziegler and Ziegler -Natta mixed catalyst;
(vii) water gas shift reation (WGSR); (viii) production of synthetic gasoline in Mobil process (i.e.
ZSM-5 Catalyst) and in Fischer-Tropsch process; (ix) deuteration of benzene; (x) Use of Collman's
reagent, Na2[Fe(CO)4] in organic synthesis.
B. Justify or criticise the following statements
ry
1. Generally the 16e-orgametallics adopt the associative path while the 18e-organometallics adopt
the dissociative path in the ligand substitution process.
ra
2. Organometallic compounds of 18e-count sometimes may adopt the associative path if they con-
tain the nonleaving ligands like 116-C6H6; 115-Cp, 113-allyl or NO.
ib
3. The rate of carbonyl substitution reaction depends on the nature of phosphine derivatives present
yl
as the spectator ligands. The rate follows the sequence:
Spectator ligand: PF3 » P(OAr)3 ) P(OR)3 ) P(Ar)3 ) PR3
m
4. In [M(CO)5L] (L = n-donor ligand), the vc-o (trans-to L) is less than vc_o(cis - L).
• For [Mn(CO)5X], vc - o increases in the order, X = CI ) Br ) I and reactivity order of CO
he
substitution is: X = CI ) Br ) I; the substitution product is mainly of cis-configuration.
5. In [MnBr(CO)5] C 4v symmetry), the four equatorial CO groups are more labile than the axial CO
group (trans to Br). lc
6. [MnBr(CO)5] is more reactive than [Mn(CO)6]+ in carbonyl substitution reactions.
ea
7. Carbonyl substitution process in [MnBr(CO)5] is stereospecific.
i.e. [Mn(Br)(CO)5] + L ~ cis-[M(Br)(CO)4(L)] + CO
th
8. [Cr(CO)5(PPh3)] is more reactive than [Cr(CO)6] in the carbonyl substitution process.

9. The 18e-complex [M(CO)6] can experience CO substitution through the electron transfer chain
e/
(ETC) under the condition: the entering ligand (L) should be a poorer n-acceptor ligand than CO.
or, [M(CO)6] should be a better electron acceptor than the product [M(CO)5(L)].
t.m
10. [LM(CO)o] + L' ~ [LL'M(CO)o_l] + CO, (L' may be also CO).

The above process shows a two term rate law. A similar two tenn rate law also prevails in the
ligand substitution reactions of the square planar complexes. But, the origins of these two rate
e
laws are different in two cases.

11. [Ni(CO)4]' [M(CO)6] (M = Cr, Mo, W) experience the dissociative path in carbonyl substitution
er
reactions.
H
• The metal carbonyls easily experience the photochemical substitution.

12. [M(CO)6] + L ~ [M(CO)5(L)] + CO; M = Cr, Mo, W; L = CO, PPh 3. There are two parallel paths
k
of reactions - k1-path (Le. first-order path) and k2 -path (i.e. second order path).
Mr(k 1) ) Mr(k2); ~(kl) ) ~S*(k2)·
lic
• Among these, the Mo-complex reacts fastest. (Hints: Compare the VM-C values; cf Q. 40,
Chapter 9).
C
13. The 18e organometallics like [Mn(115-Cp)(CO)3], [Rh(115-Cp)(CO)2] adopt the associative path in
carbonyl substitution reactions.
14. Ring slippage in [(116-C6H6)Mo(CO)3] can introduce the associative path in ligand substitution.
15. [W(CO)4 (NO)X] -~o) [W(CO)3 (NO)(PPh 3 )X J, L = PPh3 or PR3
Rate law = k1[Complex] + k2[Complex][L].
°
k2 ::::: for L = PPh3; both k 1 and k2 contribute for L = P(n-Bu)3 .
• For the k1-path: ~H;t follows the sequence (X) = 1 ) Br ) Cl.
• ~s;t (k 1) is positive while ~s;t (k 2) is negative.
16. Olefin exchange rate is faster in [Pt(C 2H4 )CI 3]- (Zeise's salt anion) than that in [(1l5-Cp)Rh(C 2H4)2]'
17. In many cases, nucleophiles can attack on the C-centre of the coordinated CO group.
18. Fischer carbene complex can be prepared in the following route:
LiCH R 0+BF - 4
[ M ( CO ) 6 ] 3 ----t) A - - -3 - - - t ) Fischer Carbene
ry
/p /R
19. M = C \... (Fischer Carbene); M = C \. (Schrock Carbene)
ra
X R
ib
In the above two carbene complexes, nature of the metal centres and nature of the carbene
substituents are different.
yl
20. 'M-C' bond length in Fischer carbenes is longer than that in Schrock carbenes.
21. Fischer carbene considers the binding of a singlet carbene that acts as a n-acid ligand while
m
Schrock carbene involves the binding of a triplet carbene that makes an ethylenic type linkage
he
with the metal centre.
22. In Fischer carbene, the nucleophilic attack occurs on the carbon carbene centre while in Schrock
carbene, it should occur on the metal centre.
23.
lc
Generally, Fischer carbenes act as the electrophiles but by changing the nature of substituents on
ea
carbene carbon, it may fail to act as an electrophile.
24. "Carbene - C is an electrophile in Fischer carbene while carbene - C is a nucleophile in Schrock
carbene"-this can be explained by frontier molecular orbital (FMO) diagram.
th
25. M=CH2 linkage in Schrock carbene is comparable to phosphorous ylids like Ph3P=CH2.
26. O=C group in R 2C=O can be substituted by H2C C in the reaction with Schrock carbene,
e/
M=CH 2·
t.m
27. Schrock carbene, M=CR2 may be described as the alkylidene complexes bearing the dianionic
.0 2
ligand: CR 2- .
28. Tebbe's reagent is functionally equivalent to [(1l5-Cp)2Ti=CH2] (a Schrock carbene) from which
e
the 'CH 2' group can be transferred in organic synthesis.

er
29. Carbyne complex can be prepared from the Fischer carbene.

30. Many metal carbonyls can act as the nucleophiles and Bronsted bases. .
H
31. [Fe (CO) 4 ]2- + H+ ~ [HFe (CO) 4 ]-. Structures of the base and its conjugate acid are different.
32. Nucleophilic character of the metal carbonyls can be utilised to generate the metal-metal bond.
k
33. Metal basicity and nucleophilicity of the following carbonyls run in the sequence:
lic
[(Cp)W(CO)3]- ) [(Cp)MO(CO)3]- ) [(Cp)Cr(CO)3]-

34. Replacement of a 'CO' group by PR3 enhances the necleophilicity and metal basicity.
C
2046
V e- o : 2003,2071 2005, 1950
(cm- I )
• The step-wise substitution (L = PPh 3) reaction cah be followed by the decrease of intensity
(for Yeo) at 2046 cm- I with the concomitant increase at 2003 and 2071 cm- I , followed by
slower decrease at 2003, 2071 cm- I with the concomitant increase at 2005, 1950 cm- I ; ....
• The step-wise rate constants decrease with the decrease of ve-o i.e. k I ) ) k 2 ) ) k3•
36. The so-called CO-insertion reaction can be considered as the carbonylation reaction.
ry
ra
The above carbonylation reactions are basically the migratory reaction where the CH 3-group
migrates. .
ib
yl
m
The possible pathways-carbonyl insertion and methyl migration can be distinguished by
he
considering the isotope labeling experiment and stereochemical analysis of the product.
39. The photochemical decarbonylation of [(1l5-Cp)Fe(CO)(PPh3)(COEt)] leads to an inversion of
lc
configuration. This observation supports the alkyl migration process and opposes the CO-group
insertion concept.
ea
40. Decarbonylation of CiS-[H 3C - C- Mn (* CO)(CO)4] through the CO-insertion pathway and
th
. II
o
e/
CH 3-migration pathway give the different stereochemical results.

t.m
o co co
CH o co.~ o~ I ;co o~ I ;co
o~ I ;;co ~ I/ ""-.CH Mn Mn
e
+ +
oc/ I "'c~o
+CO
41. Mn ~
/M1n", H3C - C / I "'co
er
3
oc/ "'co
co
I OC
CO
CO ~ CO
0
CO \
CH
H
(500/0) 3
k
42. The rate of carbonylation reaction leading to generation of the R- C- group (as a ligand)
lic
o
"
C
depends on the nature of R.

43. Olefin insertion into the M - H bond passess through a cyclic transition state.
44. M - R+ )c=c( ~ M - r-r-

I I
R. (R = alkyl group or H)
Mechanistically the process goes through the migration of R. The ease of migration follows the
sequence:
R = H ) ) CH2(CH2)nCH3 (n ~ 2) ~ CH2CH3CH3 ) CH3 ) CH2CH3
,,/ I I
45. M-R+ /C=C\. ~M-T-T-R.
Migration of R(= H) is much more favoured than migration of an alkyl group.
a p /H
ry
46. M-CH2-CH2-R~M-H + H 2C=C"
R
ra
The forward reaction is called ~-hydride elimination while the backword reaction is called olefin
ib
insertion into the M-H bond. Both the processes pass through a common cyclic transition state.
• The ease of ~-hydride elimination depends on the nature of R.
yl
o
m
/Rfl II /R"
M-C~R' + 802 M-S-C-R'
he
47. -----:l~~
R II
o "'R
lc
S02 insertion into the M-C bond leads to an inversion at the C-centre.
ea
48. Decomposition of permethyls like [W(Me)6] releases CH4 through a-H abstraction.
[WMe6] ~ [W(CH 2)3] + 3CH4
th
• 'M = CH 2 ' fragment represents the Schrock carbene moiety.

49. The following oxidative addition may be described as an insertion of L4M into the X-Y bond.
e/
X
L4 Mn + + X- Y~ L4 Mn + 2 /
t.m
(16e) '\ y
(18e)
50. Square planar complexes of the lfS-system are prone to oxidative addition.
e
51. For the square planar complexes of d 8-system of Gr. 8, 9, 10, the ease of experiencing the oxidative
er
addition increases for the heavier congeners in a group.

52. In the oxidative addition of CH3-X to a metal complex, the nucleophilicity of the metal centre is
H
quite important.
53. Trigonal planar complexes (16e) of .d lO systems also responds to the oxidative addition.
k
54. Generally oxidative addition leads to 2e-oxidation of the metal centre but examples of oxidative
lic
addition leading to 1e-oxidation of the metal centre are known.
55. [Co(CN)S]3- +R-X :~:i:;~:e )product.

C
• The reactivity order: R-I ) R-Br ) R-Cl.

• The above reaction may be applied to synthesise R-C N. ==
56. [CO(CN)5]3- can act as a catalyst for hydrogeneration of olefin.
57. Addition of dioxygen in Vaska's complex is also an example of oxidative addition without the
0-0 bond cleavage.
58. trans-[ Ir(CO)(PPh 3 )/X)](Vaska's complex)~[Ir(CO)(02)(PPh 3 )2 X]

In the product, for X = CI, it is Ir(II) while for X = I, it is Ir(III).
• Oxidative addition of different ligands to Vaska's complex can be followed by the increase of
v eo value.
• Irreversible oxidative addition to the Vaska's complex is indicated by the large increase of v eo
value.
• Stabiliy of the adducts [Ir(CO)2(PPh3)2X] follows the order, X = I ) Cl.
• For X = CH3 and I, O2 binds irreversibly but it binds reversibly for X = Cl.
ry
• Vaska's complex + RX ~ products. The stereochemistry of the products can be identified by
the VIr-Cl values. For RX = CH 3CI, the product shows V Ir-Cl = 305 cm- 1, 260 cm- 1; for RX =
ra
CH 3I, the product shows only VIr-Cl = 300 cm- l •
ib
59. At the limiting condition, addition of olefin may lead to 2e oxidation of the metal centre. It
happens so for the olefin like C 2(CN)4.
yl
60. Oxidative addition of the C-H bond may lead to the intramolecular cyclometallation.
m
x
61. M + X-X~M( (cis-addition)
he
X Oxidative addition.
X_Y~M/X(predOminant, J
M +
"y product, trans lc
ea
62. Oxidative addition of H 2 does not experience much isotope effect when 'H' is replaced by 'D'.
H-X
th
63. trans-[lr(CO)CI(PPh 3)2] .. ..~ Both cis- and trans-addition

(oxIdatIve addition
in polar media)
e/
H-X
I
---------"""'I~. Exclusively cis-addition
t.m
(oxidative addition in nonpolar media)

H-X = Hel, HBr.
64. [ML 4 ](16e) R-X) Oxidative addition product. The process goes through the associative path.
e
• Reactivity order, R = tertiary alkyl> secondary alkyl> primary alkyl; X = I > Br > CI > F.
er
65. The 18e complexes like [ML4] (square planar), [MLs] (trigonal bipyramidal) can experience the
H
oxidative addition through the dissociation of one ligand L to generate the 16e-complex.
66. [LnMJ + X-V :~:i:~~:e )[LnM(X)(Y)] + [L nM(X)2] + [L n M(Y)2] + Y2 +X 2

k
The above result can be explained by considering the free-radical mechanism of oxidative addition.
lic
67. Oxidative addition can go on in three possible mechanistic pathways: concerted process, associative
path making a nucleophilic attack by the metal centre and free-radical pathway.
C
68. [L MJ+ CR 1R 2R 3X oXid.a~ive )[L M(-CR 1R 2R 3 )X]

n additIOn n
Inversion at C indicates the SN2 path.
69. [LnMJ + CR 1R 2R 3X o~i:.a~ive)
a ItlOn
oxidative additon product + racemisation of CR 1R 2R 3X
• It supports the operation of free-radical mechanism.
70. Reductive elimination is described as 1, 1- or geminal elimination.
71. Activation of the C-H bond can be done through the oxidative addition.
72. Oxidative addition of R-H may lead to functionalisation of hydrocarbons.
73. Oxidative addition of R-H on the metal complex can lead to activation of the C-H bond. The
metal complex should have the following featuress:
coordinatively unsaturated, low oxidation state, lls-CsMes (i.e. l1s-Cp*) instead of l1s-CsHs (i.e.
unsubstituted Cp) as a ligand.
74. Monomeric [Ti(l1s-Cp)2] does not exist.
75. For the oxidative addition of R-H, the complex [(l1s-CsMes)M(PMe3)] is a better choice than
ry
[(l1S-CsHs)M(PMe3)] (M = Rh, Ir).
"
ra
76. /
LnM-R'+7C-H~LnM-C" + R'''':'-H
ib
(Functionalisation of hydrocarbons).
yl
s
77. C 6 H 6 + [(11 S -CsMe s )Rh (H)(PMe 3 )(C 3H 7 ) J;::=: C 3H g +[(11 -CsMe s )Rh (H)(PMe 3 )(Ph)]
m
The equilibrium constant for this functionalisation of hydrocarbon is very high (::::: 107).
he
78. Sometimes, activation of the C-H bonds of the phenyl groups present in the PPh 3 ligand may
lead to cyclometallation.
lc
79. Agostic interaction by the C-H bond and oxidative addition of the C-H bond are the two
limiting situations of the same process. In some complexes, these two interactions may remain in
ea
an equilibrium.
80. When the oxidative addition of the C-H bond is not possible (as in the case of £to-system), it may
th
be activated through the a-bond metathesis.

81. [(l1s-CsMes)2M-CH3] + 13CH4 ~ [(l1s-CsMes)2M-13CH3], (M = Lu, Y),
e/
• the process passes through a 4-membered cyclic transition state involving the a-H transfer,
• for the activation of the C-H bond of CH4 in the above reaction, the solvent should not
t.m
contain the C-H bond,

• if the reaction is carried out in cyclohexane solvent, the C-H bond of the solvent is not
activated.
e
82. Al2Me6 is a fluxional molecule. At room temperature, it shows only one PMR signal while at low
er
temperature it shows two PMR Signals.

83. Scrambling of the Me-groups in Al2Me6 occurs through the dissociation of the dimer to monomers
H
at the rate detennining step followed by the recombination of the monomers.

84. Activation energy (~E*) for scrambling of the Me-groups in Al2Me6 is very close to the following
k
Me-group exchange reaction.

lic
Al 2Me 6 +M(Me)2Me*~AIMe5(Me*) + MMe 3 ,(M=Ga,In)

85. All the fluxional molecules are stereochemically nonrigid bull all the stereochemically nonrigid
C
molecules are not fluxional.

• For PCI 2F3, at very low temperature, the 19F-NMR spectrum shows a double doublets and a
double triplets but at the relatively higher temperature, it shows a doublet only.
• For the ethylenic protons in [(l1s-Cp)Rh(112 -C 2H4)2], at very low temperature two PMR signals are
noted but at the relatively higher temperature, only one signal is noticed.
• For A12Me6, at low temperature, there are two PMR signals (1:2 intensity ratio) but at high
temperature, it shows only one PMR signal.
86. For the stereochemically nonrigid molecules, ~Go for the interconversion among the configurations
may not be always zero.
87. [Ni(PR3)2X2] (X =halogen) is an example of the stereochemically nonrigid molecule but it is not
an example of the fluxional molecule.
88. [Ni(CN)s]2- represents the case of stereochemical nonrigidity but not the case of fluxionality.
89. Polytopal isomerism does not represent the case of fluxionality.
90. Infra-red and Raman spectroscopy indicate two types of CO groups in [Fe(CO)s] while 13C-NMR
studies (at room temperature) show only one type of CO in [Fe(CO)s].
ry
91. For the studies of stereochemical nonrigidity, NMR spectroscopy is generally applied.
92. For NH 3, the inversion rate is tremendously high.
ra
93. AR 1R 2R 3 (A = N, P, As) can be resolved depending -on the size of R-groups.
94. Trigonal bipyramidal species are very often stereochemically nonrigid.
ib
95. Stereochemical nonrigidity is generally absent in the octahedral complexes.
yl
96. [M(H 2)(PR3)4] (M = Fe, Ru; R = Ph, OEt) is an octahedral complex. However it shows the
stereochemical nonrigidity through a nondissociative path.
m
97. Octahedral tris-chelate M« :))3
he
having the small bite distance (i.e. small twist angle) can show
the stereochemical nonrigidity through Bailer twist.

lc
Fe«:)C-NEI
ea
98. The tris-chelate, 2) 3 is highly distorted towards the trigonal prismatic con-
th
figuration at the ground state and it shows the stereochemical nonrigidity.

99. Stereochemical nonrigidity in the coordination compounds of coordination number 6 is a case of
e/
exception while the stereochemicat!igidity is a case of exception in the coordination compounds

of coordination number greater than 6.
t.m
100. 5-coordinate complexes (tbp) are very often stereochemically nonrigid where square pyramid is
the short lived geometry for the interchange of two types of ligands of the tbp structure.
101. Dodecahedral complexes are generally stereochemically nonrigid. Here for the interchange be-
e
tween the two types of ligands, cube or square antiprism is the intermediate structure.
er
10'2. Coodination compounds with coordination greater than 6 very often experience the facile polytopal
rearrangement.
H
103. Internal rotation of cyclic polyenes as in [Fe(llS-Cp)2] can lead to fluxionality.

104. Rearrangement of a-bonded polyenes as in [(1l1-Cp)GeMe3]' [(1l5-Cp)(1l1-Cp)Fe(CO)2] can lead
to the fluxional behaviour due to ring-whizzing of the (lll-CP) moiety.
k
105. In [(llS-CP)(1l1-Cp)Fe(CO)2] there are 4 types of protons: 5-equivalent protons in 115-CP; in

lic
1l1_Cp, there are three types of protons in the ratio 1:2:2. But at room temperature, the PMR signal
records a single sharp line for lls-CP and another single sharp line for lll-Cp.
C
106. In [M(lll_Cp)], ring-whizzing may occur either through 1, 2-shift or 1, 3-shift. These two
possibilities can be distinguished by analysing the IH-NMR signals.
107. In [M(lll-Cp)], ring-whizzing through 1, 2-shift and 1, 5-shift are equivalent but these can be
distinguished in the [M(11 1-C 7H7)] system.
108. I.R. data support the structure [Hg(1l1-Cp)2] but the IH-NMR spectra apparently support the
structure [Hg(lls-cp)2] in which there is only one type of proton. In fact, even at -70°C, it shows
only one sharp line in the PMR spectrum.
109. Ring whizzing may also occur in the complexes like [(1l4-COT)Ru(CO)4], [(11 4-COT)Cr(CO)3]
where COT = CgHg· IH-NMR spectra for [(1l4-COT)Ru(CO)4] show only one signal at room
temperature while it shows 4-signals for 4-different types of protons at very low temperature (ca.
-150°C).
110. Fluxionality arises through the 113- 11 1-11 3 process in the 113-allyl complexes.
111. In a [M(1l3-allyl)] complex, at relatively higher temperature, it records two PMR signals but at
very low temperature, it records three PMR signals (two doublets and one multiplet).
112. In the adduct formed by tetramethylallene and [Fe(CO)4]' at relatively lower temperature there are
ry
3 types of PMR signals while at high temperature, it shows a single signal.
113. PMR spectra of [Ti(Cp)4] are recorded at different temperatures:
ra
At 62°C, 1 signal (i.e. one type of proton); at -27°C, two signals of equal intensity; at -80°C, one
signal remains unchanged but the other signal splits into three signals.
ib
These NMR data can help us to predict the structure of [Ti(Cp)4].
yl
• [Ph - C = Cr (CO)5 ] (Fisher carbene), shows two PMR signals for the CH 3-group at a low
I
m
temperature but it shows only one signal at the higher temperature.
OCH 3
he
114. [Sc(1l5-Cp)2(1l1-CP)] is a fluxional molecule and its IH-NMR spectrum changes with the lower-
ing of temperature from ~ 30°C at which only one signal exists.
lc
115. Scrambling of the bridging and terminal carbonyl groups in di- and polynuclear metal carbonyls
ea
leads to fluxionality.
116. Carbonyl scrambling in dinuclear and polynuclear systems occurs through a concerted process.
117. [(1l5-Cp)2Fe2(CO)4] exists in solution as an equilibrium mixture of their cis-trans-isomers. At low
th
temperature (ca. -70°C), the PMR spectra record two signals while at relatively higher tempera-
e/
ture (ca. 30°C), the two signals merge into a single one.
118. cis ~ trans isomerisation in [(1l5-CP)2Fe2(CO)4] may occur theoretically in two ways with the
t.m
concomitant carbonyl scrambling and without the carbonyl scrambling.

119. The mechanistic paths leading to Me-group scrambling in Al2Me6 and CO-group scrambling in
[(1l5-Cp)2Fe2(CO)4] are different.
r
e
120. Fluxional molecule, [Rh4(CO)12] experiences the rapid scrambling of all these 12-CO groups.
er
13
121. The C-NMRspectrumof e(CO)3(:))] WhereC: = Me 2 P-C2 H4 -PMe2 showsone
H
signal which is a 1 : 2 : 1 triplet.

k
122. Reactivity of a coordinated ligand depends mainly on the nature of metal-ligand bonding inter-
lic
actions.
123. Benzene ring can easily respond to the electrophilic substitution reactions (e.g. Friedel-Crafts
C
reactions) but benzene ring being 1t-bonded with the M(CO)3 group (M =Cr, Mo, W) can respond
to the nucleophilic substitution reactions.
124. Ligands coordinated to the hard metal centres are susceptible towards the nucleophilic attack
while the ligands coordinated to the soft metal centres are prone to the electrophilic attack.
125. Coordinated N 2 is more basic than free N2.
(OCbFe/~ FS0 3 H/S02 (OC)3Fell/~.,+ +_C_I-~• (OCb(CI)Fe/~

__
126.
y
b
~ ) )
H3C H3C
• The ligand protonation leads to 11 4 to 11 3 coordination with the concomitant 2e-oxidation of the
metal centre.
127. Electrophilic substitution (e.g. Friedel-Crafts reaction) on the coordinated acetylacetonate, e.g.
[M(acac)3] (M = CrIll, COllI, Rh IIl ) can occur easity. The electrophilic substitution mainly occurs
on the central C-atom.
128. The free ligand, phen experiences nitration under a drastic condition while the same ligand in
ry
[Co(phen)3]3+ experiences nitration in a much more milder condition. .
ra
129. The unreactive C-H bond may be activated through the oxidative addition of the bond.
130. Dihydrogen (H 2) may be activated through coordination with the metal centre.
ib
131. Reaction of H 2S with the free diketones produces the monothio derivatives while the reaction of
H2S with the metal (soft)-coordinated diketones produces the dithioketones.
yl
m
he
lc
132. Free amino acid like glycine cannot participate in aldol condensation with acetaldehyde to produce
ea
threonine but the coordinated
\
glycinate can perform the task.
H
i "
OH
th
H2N /
C-H (reaction does not occur)
e/
CO- CH 3
2
t.m
(thr)
[CU(gIY)2] -OH, CH 3CHO ~ [Cu(gly)(thr)] (reaction occurs)
,
e
er
/
133.
~. <5'>-0" <N-©C
H
_R_'-N__H?
(transamination) ~=N;c 0 0
k
H/ "R'
lic
Imino complex of Cu(lI)

C
3+
Mel ~ Similar substitution

on the other chelate rings
135. Cylopentadienyl rings of ferrocene, [Fe(1l5-Cp)2] easily respond to electrophiles.
136. Fe ( 11 5 -Cp ) 2 ] CH 3 COCI+AICI 3

( .) )
•
Mono-substItuted product ( maJor.
• ) The reIatlve
· proportIons
. 0
f
[ acetylatIon
the products:
mono-substituted » 1, l'-qjsubstituted » 1, I-disubstituted
(i.e. substitution on (i.e. substitution on
ry
both rings) . the same ring)
ra
137. 1, 1'-disubstituted product of ferrocene is a single compound (i.e. without any isomer)
CH 3COCI + AICI 3
ib
138. [Fe(1l5-Cp)2] ~ Mixture of products
yl
(CH 3CO)P + H3PO. _
~------"""i_~ Only monoacetyl product.
m
5 ) ] R-CI+AICI 3
139. [ Fe ( 11 -Cp 2 - - - - - - - + ) Dialkylation homoannularly.
he
140. Both Cp- and C6H6 possess 61t-electrons, Cp- ring in ferrocene can respond to Mannich reaction
(i.e. aminomethylation) but free benzene fails to respond to this reaction.
lc
141. Cp-rings of ferrocene are more comparable to free phenol and thiophen than to benzene.
ea
142. Nitration and halogenation on the Cp-rings of ferrocene cannot be done directly. These deriva-
tives may be prepared through the lithio derivatives.
th
143. Ferrocene can stabilise the carbonium ion.

144. The following reactions support the view, stabilisation of carbonium ion by ferrocene.
e/
/OAC
t.m
Hydrolysis
(l1 S-C Pl F e - @ - - C - R ~ ,very fast reaction
(-ACOH)
""H
e
er
H
145. Ferrocenyl group is a powerful electron pushing group.

k
146. Aminoferrocene) Aniline, (Base strength)

lic
• Ferrocene carboxylic acid ( Benzoic acid, (Acid strength).

C
S
• [(l1 - C SH4 -NH 2 )Mn(COl 3 ] < @ - N H 2 < [(l1s-CsHs)Fe(T1S-CsH4-NH2)] (Base strength)
6
• @ - N H 2 > [(T1 -C 6 Hs -NH 2 )M(CO)3]. (M =Cr. Mo. W). (Base strength)
147. Acetylation and mercuration reactions of ferrocene are much faster than those of benzene.
148. Ferrocene undergoes protonation on the metal contre in a strongly acidic condition.
149. The tricarbonyl metal fragment M(CO)3 (M = Cr, Mo, W) can activate the unsaturated hydrocar-
ry
bons towards the nucleophilic attack.
Hints: Unsat\lrated hydrocarbons act as n-donor ligands; presence of strong n-acceptor ligands
ra
like CO in th~ M(CO)3 fragment.
ib
150. Among the metal-coordinated unsaturated hydrocarbons, the sensitivity of the unsaturated hydro-
x)()C)
carbons towards the nucleophile follows the sequence.
yl
(Q) ) [Q]2-
m
» ~- ) <[ ) (9) )C H; he
lc 7
ea
th
<f>
e/
tJMO
t.m
151.
y + Nu- -----t~~ Nucleophilic attack preferably on 114-diene.
e
er
<f>
H
~r~co+
k
Nu- -----i~
.. Nucleophilic attack preferably on 112-olefin.
lic
co
C
152. Hg 2+ can catalyse the hydration of alkyne.

153. Cp-rings in [Fe(115-Cp)2] do not respond to the nucleophiles but Cp-rings in [Co(115-Cp)2]+ respond
to the nucleophilic attack.
P Ph 3C+BF4-
• [(11 5 - Cp)(OC)2Fe - CHR'- CH 2R] :::::::;c::;=====:::::::=
ry
ra
ib
yl
m
he
H
H
lc
ea
(115-coordination)
(i.e., BH;)
th
Mn(CO)3
e/
t.m
e
er
H
k
lic
C
• [M(CO)6J~[M(CO)5LJ+CO;M=Cr,Mol W
• [Fe(CO)5J~[Fe2(CO)9J
• [Mn2(CO)10J~[Mn(CO)~CIJ
4
ry
NHR
• M-C=N-R~M=C( (FischerCarbene)
ra
X
H R
ib
• M-N=C-R~M-N=C(
yl
X
[PdCI 4 ]2- +Ph-N=N-Ph~Cyciometa"ated
m
• product
(azobenzene)
he
~
• PhCH=CH2 [Co(CN)s]3- )PhCH2CH3
• trans - [ptCI(Me)(PEt 3 )2]~~CH4 +trans-[PtCI 2(PEt 3)2] lc

155. In the reduction of O 2, the first-step leading to O 2 puts a thermodynamic barrier (E~2/02 = -0.35 V).
ea
However, through complexation of dioxygen (0 2), this thermodynamic disfavour can be overcome.
th
156. Activation of dioxygen (02) can be done through complexation with the transition metal centres.
157. Coordinated dinitrogen (N 2) is more reactive than free N 2.
e/
158. Dihydrogen may be activated through complexation.

t.m
• [Fe 3 ( CO)12 ] +PPh 3 ) both substitution and cluster fragmentation leading to the Inononu-
clear species.
• [Ru 3 (CO)12 ] +PPh 3 ) only substitution but no appreciable cluster fragmentation.

e
er
• [Fe(CO)4]2- (Collman's reagent)~ Synthesis of different types of organic compounds.

• Dihydrogen complexes vs. dihydrido complexes: low oxidation state of the metal centre,
H
presence of good a-donor ligands and weak n-acceptor ligands will favour the dihydrido
complexes.
k
• Dihydrogen complexes (i.e. 112-H2) generally contain the strong n-acid ligands like CO, NO.
lic
• [MoH2(PMe3)S] is a dihydrido complex while [MO(CO)3H2(PR3)2] is a dihydrogen complex

(R = isopropyl group)
C
159. Activation of dihydrogen may be done by the metal complexes through the both the homolytic
fission and heterolytic fisson of the H-H linkage.
160. Negative catalysts are basically the catalyst poisons.
161. There are both disadvantages and advantages in homogeneous and heterogeneous catalysts.
162. The so called Wilkinson's catalyst, [RhCI(PPh3)3] is actually the effective catalyst precursor.
163. In hydrogenation of olefin, Wilkinson's catalyst [RhCI(PPh3)3] cannot be replaced by [RhCI(PEt3)3]
or [IrCI(PPh 3)3].
164. In the activity of Wilkinson's catalyst, oxidative addition of H 2 and migratory insertion of
coordinated olefin into the Rh-H bond are the two important steps.
165. Wilkinson's catalyst (active form) is regenerated through the reductive elimination of alkane.
166. Wilkinson's catalyst cannot be applied for hydrogenation of all types of olefins.
• Wilkinson's catalyst can lead to the selective hydrogenation.
• Ethylene cannot be hydrogenated by using Wilkinson's catalyst.
167. Vaska's compound, i.e. trans-[lr(CO)CI(PPh 3)2] undergoes oxidative addition of H 2 but this complex
cannot be used as a hydrogenation catalyst.
ry
168. By using the modified Wilkinson's catalys~ bearing the chiral phosphine ligands, optically pure
ra
compounds (e.g. L-dopa) can be prepared.
169. Hydroformylation reaction (i.e. oxo process) should be better described as the hydrocarbonylation
ib
process.
170. Hydroformylation reaction can produce both the straight chain product (i.e. Anti-Markownikoff
yl
product) and branched chain product (i.e. Markownikoff product).
m
171. In hydroformylation reaction, the active catalyst is [HCO(CO)3] or [HCO(CO)4] which is generated
from the catalyst precursor, [C0 2(CO)g]. .
he
172. In hydroformylation reaction, to obtain a good yield, it requires an optimum partial pressure of
CO.
lc
173. Olefin insertion into the Co-H bond and CO insertion into the Co-R bond are the two key steps
in hydroformylation reaction.
ea
174. Reductive elimination of aldehyde regenerates the active catalyst in the hydroformylation reaction.
175. To obtian the greater yield of the straight chain aldehyde in the oxo process, the process is to be
th
~arried out in presence of PBu3.

176. Use (If the modified catalyst [HCo(CO)3(PBu3)] instead"of [HCO(CO)4] gives the better yield of
e/
the st raight chain aldehyde in the hydroformylation reaction, but the process is costly.
177. Rh-c(ltalyst is a better option than Co-catalyst in the hydroformylation reaction.
t.m
178. In th( Rh-catalysed hydroformylation reaction, [Rh(CO)(H)(PPh3)3] is the"catalyst precursor and

[Rh( :0)(H)(PPh3)2] is the active catalyst. It gives the better yield of straight chain aldehyde than
in th.~ Co-catalysed process.
e
179. In a< etic acid synthesis (Monsanto process), the active catalyst is [Rh(CO)212]- that experiences
er
the I )xidative addition of CH 3I. Then the steps are: migratory insertion of a CO group into the
Rh--C bond, CO addition followed by the reductive elimination of acetyl iodide.
H
180. In Monsanto acetic acid synthesis, iodide is the cocatalyst. No other halide can perform the task.
2r
k
[Rh(CO)2 I
181. CH 3 -C-OCH 3 +CO LiI ) Acetic acid anhydride.
lic
II
o
Methyl acetate
C
1 PdCI 2 ,CuCI 2
182 . W ac k erprocess: C 2H 4 +-0 2 )CH 3CHO
2 H 20, °2
183. In Wacker process (i.e. aerial oxidation of olefin), [PdC1 4]2- (as a catalytic species) cannot be
substituted by [PtCI 4]2-.
184. In Wacker process, Pd(ll) oxidises C 2H 4 to CH3CHO and it is itself reduced to Pd(O) which is
oxidised by O 2 to Pd(II) in presence of Cu(II)-salt as a catalyst.
185. Olefin metathesis reaction is catalysed by Schrock type carbene complexes.
• Metal carbyne complex can catalyse the alkyne metathesis reaction.
186. In terms of stereoregularity, polypropylene can have three configurations named-isotactic,

syndiotactic and atactic.
187. In preparing the stereoregular polymer, Ziegler-Natta catalyst (heterogeneous catalyst) is a better
choice than Zeigler catalyst (homogeneous catalyst).
188. Olefin polymerisation by both Ziegler catalyst and Ziegler-Natta catalyst involves the olefin inser-
tion into the metal-alkyl bond.
ry
189. Alkyllithium (R-Li+) is widely used as a catalyst in olefin polymerisation.
190. Ziegler-Natta mixed catalyst produces the high density polythene.
ra
191. Ziegler-Natta mixed catalyst produces the stereoregular polypropylene.
192. Ziegler-Natta catalyst is developed from the structure of u-TiCl 3 (polymer) on which Ti(III)-
ib
centres on the surface are partially alkylated. Thus these are coordinatively unsaturated.
yl
193. The homogeneous mixed catalyst Ti(Cp)2CI2 + AIEt2CI cannot produce the stereoregular polyolefins
but Ziegler-Natta mixed heterogeneous catalyst can perform the task.
m
194. Water gas shft reaction (WGSR) is industrially very much important.
195. In WGSR, catalysis probably involves the formation of metal carbonyls followed by the nucle-
he
ophilic attack by H 20 on the coordinated CO group giving rise to the M-H linkage.
196. Aluminosilicates can act as the good acid catalysts in many organic reactions.
lc
197. ZSM-5 catalyst is used to prepare the synthetic gasoline, i.e. CH 30H ZSM-5) Synthetic gasoline.
ea
198. Production of synthetic gasoline in Fischer Tropsck process probably involves the carbide carbene
mechanism.
th
199. In Fischer-Tropsch process, the platinum metals like Ru, Rh, Pd, Os, Ir and Pt are not the good
catalysts but Fe and Ni are the good catalysts. Between Fe and Ni, iron is a better catalyst.
e/
200. In Fischer-Troposch process aiming to prepare the relatively long chain hydrocarbons, iron is a
good catalyst but for methanation leading to SNG nickel is a good catalyst.
t.m
201. [(1l5-Cp)2[TaH 3] can c~talyse the deuteration of benzene (i.e. C6H 6 to C 6D 6 ).
202. trans- [PtCI (Me) (PEt 3 )2 ] +HCI) trans- [ PtCI 2 (PEt 3 )2 ] + CH 4

e
The reaction experiences an oxidative addition followed by the reductive elimination.

er
Rate = {k][H+] + k2[H+][CI-]}[complex].

203. In the adducts of Vaska compound with O 2 and C 2(CN)4, positions of the PPh 3 ligands are
H
different.
204. Tebb's reagent (Schrock carbene) mimicks the. Wittig reagent in organic synthesis.
k
205. Na2[Fe(CO)4] (Collman's reagent) mimicks the Grignard Reagent in organic synthesis.
lic
C
C
lic
k
H
er
e
t.m
e/
th
ea
lc
he
m
yl
ib
ra
ry
APPENDICES
APPENDIX I
Units and Conversion Factors
ry
Table 1: Basic physical quantities in 81 units
Physical quantity Symbol for quantity Name of unit Symbol for unit
ra
Length metre m
Mass m kilogram kg
ib
Time t second
Electric current I ampere A
yl
Temperature T kelvin K
Amount of substance mole mol
m
Luminous intensity candela cd
he
Table 2: Derived physical quantities in 81 units
Physical quantity Name of S1 unit

lc
Symbol and definition Named after
ea
ofS1 unit
Force, weight newton (N) N = kg m s-2 = J m- I Isaac Newton (1642-1727)

th
Work, energy, joule (1) J=N m James Prescott Joule (1818-1889)

quantity of heat
W = J s-I
e/
Power watt(W) James Watt (1737-1819)

Pressure pascal (Pa) Pa = N m-2 B. Pascal (1623-1662)
Electrical charge coulomb (C) C=As Charles Auguste de Coulomb (1736-1806)
t.m
Electrical potential volt (V) V = kg m2 s-3 A-I Allesandro Volta (1745-1827)

=JA-Is-I
=J C-I =W A-I
Electric capacitance farad (F) F = C V-I Michael Faraday (1791-1867)
e
Electric resistance ohm(Q) Q = V A-I Georg Simon Ohm (1787-1854)

er
Electric conductance siemens (S) S = Q-I W. von Siemens (1816-1892)

Magnetic flux weber (Wb) Wb=Vs W. Weber (1804-1891)
T = Wb m-2
H
Magnetic flux density tesla (T) Nikola Tesla (1856-1943)

Inductance henry (H) H=VsA-1 Joseph Henry (1799-1878)
Frequency hertz (Hz) Hz = S-I Heinrich Hertz (1857-1894)
k
Radioactivity becquerel (Bq) Bq = S-I A. Henri Becquerel (1852-1908)

lic
Absorbed dose of gray (Gy) Gy = m 2 S-2 Louis H. Gray (1905-1965)

radiation = J kg-I
Area (A) square metre m2
C
Volume (V) cubic metre m3

Density (p) kilogram per kg m- 3
cubic metre
Velocity (u, v, w, c) metre per second
Acceleration metre per square
second
*Concentration (c) mole per cubic metre mol m-3
*for concentration (c ) in mol per litre, it is given by mol dm-3
A.1
A.2 FUNDAMENTAL CONCEPTS OF INORGANIC CHEMISTRY
Table 3: 51 prefixes
Fraction Prefix Symbol Multiple Prefix Symbol
10- 1 deci d 10 deka da
10-2 centi c 102 hecto h
10-3 milli m 103 kilo k
10-6 micro Jl 106 mega M
10-9 nano n 109 giga G
ry
10- 12 pico P 10 12 tera T
10- 15 femto' f 10 15 peta P
ra
Table 4: CG5 and 51 units for some common physical quantities
ib
Physical CGS units Sf Units
quantity
yl
Name Symbol Name Symbol
Length centimetre cm metre m
m
Angstrom (10-8 cm) A
Mass gram g kilogram kg
he
Time second sec second
Temperature celsius °C kelvin K
kelvin oK
Energy calorie
kilocalorie
cal
kcal
lc joule
kilojoule
J
kJ
ea
litre-atmosphere ergs lit-atm erg
* tonne (t) = 103 kg, lb =453.59 g, Btu = 1.055 X 10 10 erg = 252 cal
th
Table 5: Conversion of CGS units to 81 units

e/
Physical quantity Relation between the units

Length Angstrom (A) = 10- 10 m = 10- 1 nm = 102 pm
t.m
micron (f.!) = IQ-6 m

Volume lIitre (L) = dm 3
Force dyne = 10-5 N
Energy* erg = 10-7 J
e
cal = 4.185 J
er
eV = 1.602 x 10- 19 J; eV/molecule = 96.484 kJ mol-I

Pressure atm = 1.013 x 106 dyne cm- 2 = 101.33 kN m-2
H
atm = 760 torr

mm Hg or torr = 133.32 N m-2
bar (106 dynes/cm 2 ) = 105 N m- 2
k
Viscosity poise = 10- 1 kg m- I S-I

lic
Magnetic flux density gauses = 1Q-4 T
* I cm- I (wave number) = 2.86 cal mol-I, reciprocal centimetre is known as Kayser (K) I kK (kilo
C
Kayser) = 1000 cm- I, I eV per molecule = 23.06 kcal mol-I, I erg = 2.39 x 10- 11 kcal. I eV = (charge
of an electron) x I V = 1.6 X 10- 19 C X V = 1.6 X 10- 19 J,
1.6 x 10- 19 x 6.02 x 1023
I eV/molecule = 1000 kJ/mole = 96.488 kJ mol-I.
I kK molecule-I = 103 cm- I molecule-I
=he x 103 em-I molecule- 1 (Cf . E =hv = ~)

= 6.62 X 10-34 J s x 2.99 X 108 m S-I x 105 m- I molecule-I
= 1.985 x 10-20 J molecule = 11.96 kJ mol-I
'Table 6: Atomic Units (see text, Vol. 1, Chapter 1, Sec. 1.8.2)
ApPENDICES A.3
APPENDIX II
Some Physical and Chemical Constants
Table 1: Values of some physical and chemical constants
Constant CGS and other units Sf units
ry
Acceleration due to gravity (g) 980.665 cm sec- 2 9.80665 m s-2
Avogadro's number (NA ) 6.02217 x 1023 molecules mole-I 6.02217 x 1023 mol-I
ra
Bohr magneton (J..lB) 9.274 x 10-21 erg gauss-I 9.274 x 10-24 J T-l
Nuclear Magneton (J..l N) 5.04 x 10-24 erg G-I 5.04 X 10-27 J T-I
ib
Bohr radius (a o ) 0.52918 A 5.2918 X 10- 11 m
Boltzmann constant (k B or k) 1.3806 x 10- 16 erg (degree Kt l 1.3806 x 10-23 J K-l
yl
Debye 10- IR esu cm 3.335G X 10-30 C m
Electronic charge (e) 4.80298 x 10- 10 esu 1.60216 x 10- 19 C
m
Electronic rest mass (me> 9.10953 x 10-28 g 9.10953 X 10-31 kg
Faraday (F) 96487 coulomb equiv- I 9.6487 X 104 C mol-I
he
Gas constant (R) 8.3144 x 107 erg (degree K)-I mole-I 8.3144 J K-l mol-I"
8.31441 Joules (degree K)-I mole-I 8.3144 N m K-I mol-I
82.053 x 10-3 litre-atm (degree Kt l mole-I 8.3144 Pa m 3 K-I mol-I
Permitivity of vacuum (EO>

lc
1.987 cal (degree Kt l mole-I
8.854188 X 10- 12 C V-I m- I
ea
(C V-I m-I = C2 N-I m- 2)
Permeability of vacuum (J..l) 41t x 10-7 H m- I
Planck's constant (h) 6.62618 X 10-27 erg sec 6.62618 x 10-34 J s
th
Rest mass of proton (mp ) 1.672648 x 10-24 g 1.672648 x 10-27 kg

Rest mass of neutron (m n) 1.674954 X 10-24 g 1.674954 x 10-27 kg
Atomic mass unit (u) 1.660565 x 10-24 g 1.660565 X 10-27 kg
e/
(1 u = 10-3 kg mol-IINA) (= 931.48 MeV)

Vacuum speed of light (c) 2.99793 X 10 10 cm sec-I 2.99793 x 108 m S-I
t.m
Standard atmospheric pressure 76 cm Hg 101.325 kPa

760 mm Hg (or torr) 1.01325 bar
1.1032 x 106 dyne crv- 2
Hartree energy (E h ) 4.3597 X 10- IR J
e
Zero of the Celsius scale 273.15 K

er
H
k
lic
C
APPENDIX III
Wavelength and Colours
Table 1: Spectral wavelength and colours
ry
Range of the wavelength Colour of the radiation Complementa1y
absorbed (nm) absorbed colour observed
ra
400-450 Violet Green-yellow
450-470 Indigo Yellow
ib
470-490 Blue Orange
490-500 Blue-green Red
yl
500-560 Green Purple
560-575 Green-yellow Violet
m
575-590 Yellow Indigo
590-640 Orange Blue
he
640-730 Red Blue-green
lc
ea
th
e/
B
t.m
G
e
Artist's Colour Wheel: Colours and complementary colours.

er
Col0urs that stand opposite each other on the colour wheel are called as the complimentary colours. The amount of a colour in
H
a particular image can be decreased by increasing its complimentary colour and vice-versa.
RGB colour model: In this model, red (R), green (G), and blue (B) are considered as the three primary colours that can generate
k
all the colours of the visible spectrum when mixed together in different proportions. Mixing of these three primary colours in equal parts
gives white and complete absence of these three colours results in black. Computer monitor devices use these three additive primaries
lic
to produce the different colour shades.

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ApPENDICES A.5
APPENDIX IV
Names, symbols, atomic numbers and atomic weights* of the elements
Element Symbol Atomic Atomic Element Symbol Atomic Atomic

number weight number weight
ry
Actinium Ac 89 227.03 Lead Pb 82 207.19
Aluminium Al 13 26.98 Lithium Li 3 6.94
ra
Americium Am 95 (243) Lutetium Lu 71 174.97
Antimony Sb 51 121.75 Magnesium Mg 12 24.31
ib
Argon Ar 18 39.95 Manganese Mn 25 54.94
Arsenic As 33 74.92 Mendelevium Md 101 (258)
At Hg
yl
Astatine 85 (210) Mercury 80 200.59
Barium Ba 56 137.34 Molybdenum Mo 42 95.94
m
Barkelium Bk 97 (247) Neodymium Nd 60 144.24
Beryllium Be 4 9.01 Neon Ne 10 20.18
Bismuth Bi 83 208.98 Neptunium Np 93 237.05
he
Boron B 5 10.81 Nickel Ni 28 58.71
Bromine Br 35 79.91 Niobium Nb 41 92.91
Cd 112.40 Nitrogen N 7 14.01
Cadmium
Calcium Ca
48
20 40.08
lc
Nobelium No 102 (259)
ea
Californium Cf 98 (251) Osmium Os 76 190.2
Carbon C 6 12.01 Oxygen 0 8 16.00
Cerium Ce 58 140.12 Palladium Pd 46 106.4
th
Cesium Cs 55 132.91 Phosphorus P 15 30.97

Chlorine Cl 17 35.45 Platinum Pt 78 195.09
Chromium Cr 24 52.01 Plutonium Pu 94 (244)
e/
Cobalt Co 27 58.93 Polonium Po 84 (209)

Copper Cu 29 63.54 Potassium K 19 39.10
t.m
Curium Cm 96 (247) Praeseodymium Pr 59 140.91

Dysprosium Dy 66 162.50 Promethium Pm 61 (145)
Einsteinium Es 99 (252) Protactinium Pa 91 231.04
Erbium Er 68 167.26 Radium Ra 88 226.03
e
Europium Eu 63 151.96 Radon Rn 86 (222)

Fermium Fm 100 (257) Rhenium Re 75 186.2
er
Fluorine F 9 19.00 Rhodium Rh 45 102.91

Francium Fr 87 (223) Rubidium Rb 37 85.47
H
Gadolinium Gd 64 157.25 Ruthenium Ru 44 101.07

Gallium Ga 31 69.72 Samarium Sm 62 150.35
Germanium Ge 32 72.59 Scandium Sc 21 44.96
k
Gold Au 79 196.97 Selenium Se 34 78.96

lic
Hafnium Hf 72 178.49 Silicon Si 14 28.09

Helium He 2 4.00 Silver Ag 47 107.87
Holmium Ho 67 164.93 Sodium Na 11 22.99
C
Hydrogen H 1 1.008 Strontium Sr 38 87.62

Indium In 49 114.82 Sulfur S 16 32.06
Iodine 1 53 126.90 Tantalum Ta 73 180.95
Iridium Ir 77 192.2·, Technetium Tc 43 (99)
Iron Fe 26 55.85 Tellurium Te 52 127.60
Krypton Kr 36 83.80, Terbium Tb 65 158.92
Lanthanum La 57 138.91 Thallium TI 81 204.37
Lawrencium* Lr 103 (260). Thorium Th 90 232.04
(Contd.)
* Previously it was represented by Lw. Now as per IUPAC recommend~tion, it is represented by Lr.
Element Symbol Atomic Atomic Element Symbol Atomic Atomic

number weight number weight
Thulium Tm 69 168.93 Xenon Xe 54 131.30

Tin Sn 50 118.69 Ytterbium Yb 70 173.04
Titanium Ti 22 47.90 Yttrium Y 39 88.91
Tungsten W 74 183.85 Zinc Zn 30 65.37
ry
Uranium U 92 238.03 Zirconium Zr 40 91.22
Vanadium V 23- 50.94
ra
* Values are based on the presently accepted physical scale of 12C = 12.00000 as the standard. The ratio of these atomic weights to
those on older chemical scale assuming the value 16.00000 for the atomic weight of natural oxygen (composition: 16 0,99.757%;
ib
17 0,0.039%; 18 0,0.204%) is 1.000279. The values given within the parentheses are the mass numbers of the most commonly known
isotopes.
yl
The true atomic weight of natural oxygen is given by : 16 x 0.99757 + 17 x 0.00039 + 18 x 0.00204 = 16.00447.
m
. . Physical atomic weight = 16.00447 = 1.000279
It gl ves. Chemical atomic weight 16.00000
he
Presently the term atomic weight is replaced by atomic mass or relative atomic mass (RAM). These are expressed in terms of amu
or u or Da (Dalton). These aspects have been discussed in Sec. 5.2.3.
** For thetranslawrencium elements with Z> 103, the currently used names (cf. Chemistry of the Elements by N.N. Greenwood and
lc
A. Earnshaw and IUPAC, 1997) are: 10411f(rutherfordium), IOsDb (dubnium), 106Sg (seaborgium), 107Bh (bohrium), I08Hs (hassium),
109Mt (meitnerium). However, other names to these elements have also been suggested from time to time. These are: Z = 104
ea
(kurchatovium, Ku; dubnium, Db), Z = 105 (hahnium, Ha, neilsbohrium, Ns, joliotium, JI), Z = 106 (rutherfordium, Rj), Z = 107
(neilsbohrium, Ns), Z = 108 (hahnium, Hn). The IUPAC (1977) recommendation, i.e. a hybrid Latin-Greek numerical method (cf.
Sec. 8.6), is free from such confusions. The elements with Z = 110, Ill, 112, 114, 116, 118 have been characterised.
th
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APPENDIX V
Some Useful Mathematical Relationship
t.m
(A) Differentials
(u and v are the functions of x; a and m are constants).
e
~(au)=adu
er
dt" = 1 d du dv
(i) (ii) (iii) dt"(u+v)= dt" + dt"
dt" dt" dt"
H
(iv) ~xm =mx m- I (v) ~lnx=~ (vi)

dlnu 1 du
-----
dt" dt" x dt" udt"
k
(vii) ~(eX)=ex (viii) ~(eU)=eu du (ix)

d dv du
dt" (uv) = u dt" + v dt"
lic
dt" dt" dt"
v(~)-u(~)
C
~ (sin x) = cos x ~ (cos x) = -sin x

(x)
~(~)= v-
')
(xi)
dt"
(xii)
dt"
d ~-', -c' d
d
(xiii) - (tan x) = sec 2 x (xiv) - (sin u) = cos u ~ (xv)
d (cos U ) = - Sill
-......:. . U -du
dt" dt" dt" dt" dt"
(B) Integrals
(u and v are the functions of x; a and m are constants; for the indefinite integrals, there should be an addition of arbitrary constant
of integration).
ApPENDICES A.7
(i) Jdx = x (ii) Jaudx = a Judx (iii) J(u+v)dx= Judx+ Jvdx
xm+1
(iv) Jx
m
dx=--,(m;t-I)
m+1
(v) Jdx =In x
x
(vi) JeXdx = eX
(vii) (viii) JIn ax dx = x In ax - x (ix) Jsin x dx = - cos x
ry
Jcos Juvdx = u Jvdx - J[: Jvdx] dx,
ra
(x) x dx = sin x (xi) (by parts)
ib
Judv = uv - Jvdu
00 ,
(xii) (xiii)
Jxne-
ax
= ~I
n
' (n positive integer)
a +
o
yl
(C) Trigonometric relationship
m
(i) sin (900 - S) = cos S (ii) cos (900 - S) = sin S
he
(iii) exp (± imS) = cos (mS) ± i sin (mS), (Demovier's theorem)
cos (mS) =! (exp(imO) + exp(-imS)] sin (mS) = 2i1 [exp(imS) -

lc exp(-imS)]
2
ea
(iv) 2 2 (v)
sin S + cos S = 1 sin 2S=2sinScosS
2 2 2 2
(vi) cos 2S = cos S - sin S = 2cos S -I = 1- 2sin S (vii) sin (a ± J3) = sinacosJ3 ± cosasinJ3
th
. a . J3 = 2 sm
. "2
1 (a ± J3 ) cos "2
1 (a + J3 )
(viii) cos (a ± J3) =cosacosJ3 +sinasinJ3 (ix) sm ± sm
e/
1 1
cos a - cos J3 = - 2 sm
. "2
1 (a + J3' 1 (a - J3 )
t.m
(x) cosa + cosJ3 = 2cos"2 (a + J3) cos "2 (a - J3) (xi) ) sm "2
. . J3 1 1
(xii) sm a sm ="2 cos (a - J3) - cos (a + J3) 2" (xiii) cos a cos J3 = !2 sin (a - J3) + !2 cos (a + J3)
e
. a cos J3 = Ism
sm . (a + J3 ) + I sm
"2 . (a - J3 ) 2"
er
(xiv)
H
(0) Some Useful Expansions (r ~ 1)
(l + X}-I = 1 - x + x 2 -x 3 + ..... (l - x}-I = 1 + x + x 2 + x 3 + .... (l - x}-2 = 1 + 2x + 3x 2 + 4x 3 + ....

k
x2 3 4
lic
x x
In (I +x)=x-
2 +
3 -4" + ....
C
x2 x x 3 4
In (l-x)= -x-
2 - 3 -4" ....
x2 x3 x4
exp(x)ore X = 1 + x + - + - + - + .... , (for all x)
2! 3! 4!
2 3
-x x x
exp (- x) or e = 1- x + 2! - 3! + ....
3 5 7
. X X X
SIn X = X - 3! + 5! -7T + ...., (for all x)
2 4 6
x x x
cos X = 1- 2! + 4! - 6! + ...., (for all x)
ry
In x! = x In x - x or x! =~ (Stirling approximation, 1730)
eX
ra
(for x > ca. 10)
ib
(E) Progressions
yl
(i) Arithmatic progression: a, a + d, a + 2d, ....
m
n-th term (Tn) = a + (n - I)d;
=!!- (11 + Tn) =!2 {2a + (n -1)d}
he
Sum of first n tenns (Sn)
2 2
nO + n)
Sum of first n-natural numbers = 1 + 2 + 3 + .... + n = --2- lc
ea
(ii) Geometric progression: a, ar, ar2, ....
n
a(1- r )
n-th term (Tn) = am - I; =- - - when r < 1
th
Sum of first n terms (Sn)

(1- r)
e/
n
a(r -1)
Sn =~ when r> 1; sum to infinity (Soo) = 1: r when Irl < 1
t.m
(iii) Useful results:
n
e
~
~ x
2 n
= - (n + 1) (2n + 1)
x=1 6
er
For first n natural numbers, 1, 2, 3, ...., n

:;1 x 3= %(n + I) ]2
n [
H
(F) Permutations and combinations

k
lic
np =_n_!_. np =~=~=n" nC n_!_. n _ ,n . n - nC . nC = nCo =1

r (n-r)!' n O! 1 ., r - r!(n-r)!' Pr -r. C r ' Cr - n-r' n
C
n! =1 X 2 X 3 X ••.... X (n - 2) X (n - I) X n; O! =1
(G) Logarithms
log(mn) = log m + log n; log (~) = log m -log n,

n
log (m ) = n log m; log 1 = 0; loga a = 1; In(x) = 2.3 log x
Natural logarithm (base e); common logarithm (base 10).
(H) Mathematical Constants

1t = 3.14159265 ..... , e = 2.71828 ...., In x = 2.30258 ... log lOx
ApPENDICES A.9
APPENDIX VI
Books Consulted
Akhmetov, N.: General and Inorganic Chemistry Huheey, lE.: Inorganic Chemistry-Principles of Structure and
Akitt, J.W.: NMR and Chemistry Reactivity
Anantharaman, R.: Fundamentals of Quantum Chemistry Huheey, lE., Keiter, E.A., Keiter, R.L. and O.K. Mehdi: Inorganic
Aruldhas, G: Molecular Structure and Spectroscopy Chemistry-Principles of Structure and Reactivity
ry
Ballhausen, C.1.: Introduction to Ligand Field Theory lolly, W.L.: Principles of Inorganic Chemistry
Banerjea, D.: Inorganic Chemistry-Elements and Compounds 10rgensen, C.K.: Absorption spectra and Chemical Bonding in
Banerjea, D.: Coordination Chemistry Complexes
ra
Banerjee, D.: Inorganic Chemistry (Principles) Kalshi, P.S.: Spectroscopy of Organic Compounds
Banerjea, D.: Fundamental Principles of Inorganic Chemistry Kapoor, K.L.: A Textbook of Physical Chemistry (Vol. 1-4)
ib
Banwell, C.N.: Fundamentals of Molecular Spectroscopy Kettle, S.EA.: Coordination Compounds
Berrow, GM.: Introduction to Molecular Spectroscopy Langford, C.H. and Gray, H.B.: Ligand Substitution Processes
yl
Basolo, E and Pearson, R.G: Mechanisms of Inorganic Reactions Laidler, K.1. and Meiser, lH.: Physical Chemistry
Bertini, I., Gray, H.B., Lippard, S.l. and Valentine, 1.S.: Lee, lD.: Cpncise Inorganic Chemistry
m
Bioinorganic Chemistry Lever, A.B.P.: Inorganic Electronic Spectroscopy
Carlin, R.L.: Magnetochemistry Lippard, S.1. and Berg, 1.M.: Principles of Bioinorganic Chemistry
Chanda, M.: Atomic Structure and Chemical Bonding Mackay, K.M. and Mackay, R.A.: Introduction of Modern
he
Chatwal, GR. and Anand, S.K.: Spectroscopy Inorganic Chemistry
Connelly, G, Damhus, T. (Editors): Nomenclature of Inorganic Mahan, B.H.: University Chemistry
Chemistry: IUPAC Recommendations 2005. Miessler, G.L. and Tarr, D.A.: Inorganic Chemistry
Cotton, EA. and Wilkinson, G.: Advanced Inorganic Chemistry
Cotton, EA. and Wilkinson, G: Basic Inorganic Chemistry
lc
Mohan, 1.: Organic Spectroscopy: Principles and Applications.
Mukherjee, GN. & Das, A.: Elements of Bioinorganic Chemistry
ea
Cotton, EA. and Wilkinson, G., Murillo, C.A. and Bochmann, Nakamoto, K.: Infrared Spectra of Inorganic and Coordination
M.: Advanced Inorganic Chemistry Compounds
Cotton, EA.: Chemical Applications of Group Theory Orchin, M. and laffe, H.H.: The Importance of Antibonding
th
Das, Asim K.: Bioinorganic Chemistry Orbitals

Das, Asim K.: Inorganic Chemistry: Biological and Environmental Pavia, D.L., Lampman, G.M. and Kriz, GS. : Introduction to
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Aspects Spectroscopy
Das, Asim K.: Environmental Chemistry with Green Chemistry Potterfied, W.W.: Inorganic Chemistry: A Unified Approach
Das, A.K.: A Textbook on Medicinal Aspects of Bioinorganic Purcell, K.E and Kotz, J.C.: Inorganic Chemistry
t.m
Chemistry Rakshit, P.C.: Physical Chemistry

Day (lr), D.A. and Underwood, A.L.: Quantitative Analysis Rao, C.N.R.: Chemical Applications of Infrared Spectroscopy
Day, M.C. and Selbin, 1.: Theoretical Inorganic Chemistry Rao, C.N.R.: Ultraviolet and Visible Spectroscopy
Dorain, P.B.: Symmetry in Inorganic Chemistry Ray, R.K.: Electronic Spectra of Transition Metal Complexes
e
Douglas, B.E. McDaniel, D.H. and Alexander, 1.1.: Concepts and Reddy, K.V.: Symmetry and Spectroscopy of Molecules
Models of Inorganic Chemistry Shriver, D.E, Atkins, P.W. and Langford, C.H.: Inorganic Chemistry
er
Drago, R.S,: Physical Methods in Chemistry Sarkar, R.: General and Inorganic Chemistry (Part I and II)
Drago, R.S.: Physical Methods for Chemists Satyanaryana, D.N.: Electronic Absorption Spectroscopy and
Dyer, 1.R.: Applications of Absorption Spectroscopy of Organic Related Techniques
H
Compounds Satyanarayana, D.N.: Vibrational Spectroscopy - Theory and

Dutta, P.K.: General and Inorganic Chemistry Applications
k
Dutta, R.L. and Syamal, A.: Elements of Magnetochemistry Sharpe, A.G: Inorganic Chemistry
Dutta, R.L.: Inorganic Chemistry (Part. I and II) Skoog, D.A., West, D.M., Holler, F.1. and Crouch, S.R.:
lic
Earnshaw, A.: Introduction to Magnetochemistry Fundamental of Analytical Chemistry

Ebsworth E.A.V., Rankin, D.W.H. and Cradock, S.: Structural Solomon, E.I. and Lever, A.B.P.: Inorganic Electronic Structure
C
Methods in Inorganic Chemistry: and Spectroscopy

Emeleus, H.1. and Anderson, 1.S.: Modern Aspects of Inorganic Steed, l.W. and Atwood, J.L.: Supramolecular Chemistry
Chemistry Topping, J.: Errors of Observation and Their Treatment
Figgis, B.N.: Introduction to Ligand Fields Vogel, A.I.: A Textbook of Quantitative Inorganic Analysis
Glasstone, S.: Textbook of Physical Chemistry Wilkins, R.G: The study of Kinetics and Mechanism of Reactions
Griffith 1.S.: The Theory of Transition Metal Ions of Transition Metal Complexes
Greenwood, N.N. and Earnshaw, A.: Chemistry of the Elements Wulfsberg, G: Inorganic Chemistry
Acknowledgement
The above listed references and sources have been freely consulted to borrow their views and ideas. The present authors are
indebted to all these authors to an endless extent. The present author expresses his heartiest thanks and grateful acknowledgement
to all of them.
C
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k
H
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e
t.m
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th
ea
lc
he
m
yl
ib
ra
ry
Subject Index
18-Electron (18e) rule 1306, 1503 Antiferromagnetic MnO Bridging phenyl group 1415
2nd order Zeeman effect 1167 crystal 1255 Brown ring complex 1367, 1373
Antiferromagnetic substances 1099 Butadiene 1440, 1442
Antiknock compound 1420, 1423 Butadiene in metal
ry
Arene complexes 1483 complexes 1441
Aromaticity 1460
ra
a-Elimination 1528
Accidental orthogonality 1228, Aryl complex 1430
Atactic polymer 1629
ib
1238, 1251
Actinides (magnetic Azulene system 1455, 1476 Canted antiferromagnetism 1099
yl
properties) 1153 Canted ferromagnetism 1099,
Activation of C-H bonds 1545 1258
m
Activation of coordinated Carbene complexes 1430, 1513,
ligands 1578 ~-Elimination 1526, 1527 1516
he
Activation of dihydrogen ~-H elimination 1407, 1419, Carbene type compound 1431
(H 2) 1390, 1539, 1578, 1600 1430, 1526ff Carbide-carbene mechanism 1639
Activation of N2 1597 B12-coenzymes 1297 lc Carbido complexes 1518
Activation of O 2 1596 Bent double bond 1423 Carbocycles with 1t-electrons 1459
ea
Agostic interaction 1405, 1527, Bent metallocenes 1473, 1477 Carbonyi'alkyIs 1318
1548 Benzene complexes 1481 Carbonyl clusters 1300
Alkane elimination 1430, 1432 Berry pseudorotation 1556, 1570 Carbonyl halides 1301, 1314,
th
Alkyl complex 1430 Binuclear Cu(II)-acetato 1317, 1354

Alkyl migration 1521 complex 1236 Carbonyl hydrides 1300, 1301,
e/
AlkyI or aryl compounds 1401 Bis(benzene) chromium 1298 1314, 1315, 1351
Alkylidene complexes 1435, Bite angle 1185 Carbonyl insertion 1523
t.m
1514, 1517 Bleaney-Bowers equation 1235, Carbonyl scrambling 1565, 1566

Alkyne metal complexes 1447, 1287, 1290 Carbonyl-nitrosyls 1369
1450 Bohr magneton 1091 Carbonylate anions 1301, 1314,
Allyl complexes 1452 Bonding in carbonyls 1318 1315, 1351, 1503
e
Allyl rearrangement 1562 Bose-Stoner's spin only Carbonylation 1314, 1520

er
Anomalous magnetic formula 1123, 1126 Carbonyls 1299

properties 1178, 1205 Bridge bond formation 1408 Carbonyls as anions 1518
H
Antiferromagnetic Bridging and terminal CO Carbyne complex 1430, 1435,

interaction 1100, 1229 groups 1307, 1311 1517
k
1.1
lic
C
1.2 FUNDAMENTAL CONCEPTS OF INORGANIC CHEMISTRY
Catalysis by organometallic Diamagnetism 1103 Fluxional behaviour in the allyl

compounds 1608 Dibenezenechromium 1481 complexes 1454
Catalysis by transition metal Dies-Alder reaction 1463 Fluxionality 1310, 1429, 1552,
complexes 1604 Dihydrido complexes 1391 1553
Catalytic efficiency 1606 Dihydrogen and dihydrido Frankland 1297, 1425
Chauvin mechanism 1628 complexes 1390, 1600, 1601 Fullerene complexes 1445
ry
Cluster fragmentation 1511 Dihydrogen vs. dihydrido Fullerenes as ligands 1445
Collman's reagent 1353, 1406, complex 1539 Fulvalene like system 1476
ra
1519 Dimeric chromium(II) Fulvalene type compound 1297
Competitive 1t-bonding effect 1339 acetate 1253
ib
Conjugated dienes 1440 Dimeric complexes ofVO(lV) of
Cooperative magnetic interaction MoO(V) 1245, 1249
yl
in dinuclear copper(II) Dimethyl zinc 1297
Dinitrogen complexes 1386, 1597 g- factor 1103
complexes 1230
m
Dinuclear complexes of Gauss's law 1087
Cooperative magnetism 1099,
chromium(III) 1251 Geometrical frustration 1259
1236
he
Dinuclear complexes of Goodenough-Kanamori-Anderson
Copper(II) accetate 1230
titanium(III) 1251 rules (GKA Rules) 1206, 1220,
Coupling constant (J) 1206
Dinuclear copper(II) 1225
Criticall0Dq 1175
Curie constant 1098
lc
complexes 1236, 1244 Gouy magnetic balance 1110
Grignard reagent 1297, 1353,
ea
Curie equation 1098, 1280 Dioxygen complexes 1596
Disilenes 1422 1408
Curie temperature 1099
Grubbs catalyst 1628
Curie-Debye equation 1091
th
Gyromagnetic ratio 1102

Curie-Weiss equation 1098
Cyanido complexes 1375
e/
Cyclic Polyenes 1459, 1460,

Eighteer.. electron (18e) rule 1299
1561
t.m
Electron transfer chain (ETC)

Cyclobutadiene complexes 1461 Hapto-nomenclature 1299
reactions 1507
Cycloheptatriene 1484 Haptotropic shift 1477, 1482
Electrophilic attack on the
Cycloheptatrienyl complexes 1484 Heisenberg-Dirac-van Vleck
coordinated ligands 1575
(HDvV) equation 1206
e
Cyclometallation 1547
Exchange energy 1177
Cyclooctatetraene (cot) 1485, Helerocycles 1478
er
Exchange Hamiltonian 1206

1486 Heterocyclic arene 1483
Cyclooligomerisation of Heterogeneous catalysts 1606
H
acetylenes 1635 High-spin low-spin cross-over

Cyclopalladation 1548 point 1175
k
Cyclopentadienyl complexes 1411, Homogeneous catalysts 1606

Ferrihemeproteins 1186
Homoleptic products 1306, 1348
lic
1423, 1429, 1463, 1480 Ferrimagnetism 1256

Huckel's rule of aromaticity 1459
Ferrites 1257
Hydrocarbonylation process 1614
C
Ferrocene 1297, 1298, 1464,

Hydroformylation reaction 1614,
1474, 1584, 1585
1620
Decarbonylation reactions 1520 Ferromagnetic substances 1099
Hydrogenation of olefins 1608,
Delocalisation factor 1138, 1173 Ferromagnetism 1100, 1225
1609
Deuteration of benzene 1641 First-order Zeeman effect 1122
Hyperconjugation effect 1418
Dewar-benzene 1463 Fischer and Schrock carbene 1512
Dewar-Chatt-Duncanson Fischer-Tropsch process 1639,
model 1437 1641
Diamagnetic substances 1097 Fisher carbene 1351
Diamagnetic susceptibility 1104, Fluxional behaviour in organo- Indenyl (lnd) ligand 1455
1106 metallic compounds 1558 Indenylgroup 1476
SUBJECT INDEX 1.3
Inert pair effect 1420, 1423 Magnetic behaviour of the Mobil process 1638, 1641
Infrared spectroscopy of metal complexes of 3d-metal Molar susceptibility 1089
carbonyls 1328 ions 1139 Molecular orbital approach
Insertion and deinsertion Magnetic dilution 1100 for the 1800 superexchange
reaction 1434, 1520 Magnetic exchange interaction 1225
Intensity of magnetisation 1087 interactions 1206 Molecular orbital approach
ry
Intermediate spin and spin-admixed Magnetic induction 1087 for the 90 0 superexchange
states 1194 Magnetic moments of the interaction 1227
ra
Intermediate spin state 1191, 1194 lanthanides 1149 Molybdenocene 1480
Intrallogons 1202 Mond 1297
Magnetic permeability 1088
Inverse spinels 1257
ib
Magnetic properties of Fe(II), Mond's process 1314
Inversion of pyramidal Monomer-polymer equilibria 1199
Co(ll), Ni(II) and Cu(II)
yl
molecules 1554 Monsanto acetic acid
complexes 1144
IR-active C-O stretching 1331 synthesis 1620
Magnetic properties of the
m
Iron-sulfur protein 1256 Multiplet and multiplet
actinides 1153
Isocarbonyl(carbonyl) gold 1313, width 1119, 1121
he
1314, 1320 Magnetic properties of the
Isocyanides as ligands 1379 complexes with the
Isomorphous dilution 1100 T-ground state 1155
Isonitrile complexes 1379
lc
Magnetic properties of the
lanthanides and actinides 1148 Natural magnetic orbital
ea
Isoprene 1631
Magnetic properties of the second (NMO) 1233
Isotactic polymer 1629
and third transition series 1166 Neel temperature 1099
Isotope effect 1416
Nephelauxetic effect 1119, 1173,
th
Magnetic properties: A, E-terms vs.

T-term 1155 1178
Nitric oxide as ligands 1357
e/
Magnetic substance 1097

Nitrogenase enzyme 1390
Magnetic susceptibility 1089
Nitroprusside ion 1372
t.m
Kinetic stability 1428

Magnetically concentrated Nitrosyl carbonyls 1368, 1370
Kotani expression 1160
systems 1229 Nitrosyl complexes 1357ff
Kotani expression for ground
T-term 1294 Mannich reaction 1583 Nitrosyl cyanides 1368
Matrix isolation 1314
e
Kotani plot 1161 Nitrosyl-halides 1368

Mercuration 1426 Nonclassical bond 1296
er
Mercurochrome (merbromin) 1428 Nonclassical carbonyIs 1341

Metal basicity 1520, 1534 Nucleophilic and electrophilic
H
Lande interval rule 1120 Metal carbene 1435 attack on the coordinated
Lande splitting factor 1120 Metal carbonyIs 1299, 1314 ligands 1570
k
Langevin-Debye equation 1100, Metal carbonyIs as Nucleophilic attack on the

coordinated CO 1572
lic
1128 nucleophiles 1518

Lanthanides (magnetic Metal framework 1348
C
properties) 1148 Metal nitrosyls 1357

Larmor precession 1103 Metal-metal bonding 1254
Lifschitz salts 1196 Metal-metal 0 bonding 1230 Octahedral - square planar
Ligand migration reaction 1520 Metallacyclobutane 1628 equilibria 1196
Lithium alkyl 1405 Metallacyclopropane 1438, 1537 Octahedral-tetrahedral
Lorenz's law and equilibrium 1204
Metallacyclopropene 1447
diamagnetism 1104 Olefin insertion 1526
Metallation 1583
Olefin metathesis 1627
Metallobiomolecules 1256 Olefinic complexes 1436, 1443 .
Metallocenes 1464, 1472 Orbital contribution from the
Jl-bond 1437 Methyl migration 1523 excited T-state 1154
1.4 FUNDAMENTAL CONCEPTS OF INORGANIC CHEMISTRY
Orbital contribution to the magnetic ,@] Spin frustration 1258, 1260

moment 1128, 1130, 1154 Spin intermediate 1186
Orbital magnetic moment 1102 Quadruple bonding 1253, 1254 Spin magnetic moment 1101
Orbital reduction factor (k) 1138, Quenching of orbital Spin state equilibrium 1178,
1173, 1175 contribution 1128 1187, 1196
Organolithium compounds 1403 Spin state isomerism in the five
ry
Organometallic compounds 1295 coordinate complexes 1191
Organometallics of alkali Spin state isomerism in the
ra
metals 1402 octahedral complexes 1179
Organometalliods 1296 Reactions of the coordinated CO
Spin state isomerism in the square
Organosilicons 1422 ligand 1511
ib
. planar complexes 1189
Organotin compounds 1424 Reactivity of the coordinated
Spin transition curves 1181, 1182
ligands 1570, 1586
yl
Orthogonal and nonorthogonal Spin-admixed ground state 1194
orbitals 1207 Reactivity of the cyclopentadienyl
Spin-only magnetic moments 1094
m
Orthometallation 1547 rings of ferrocene 1581
Spin-orbit coupling
Overlap integrals 1207 Reductive elimination 1432, 1543
components 1155
he
Oxad reaction 1529 Reformatsky reaction 1427
Spin-orbit coupling
Oxidative addition 1434, 1529 Relative permeability 1088
constants 1116, 1117, 1133
Oxido_-bridged Mo 20 r core 1247 Retrobonding 1324, 1325'
Oxidovanadium(lV) and Ring slippage 1509 lc
Ring whizzing 1429, 1560, 1561
Spin-orbit coupling
contribution 1133
ea
oxidomolybdenum(V) 1248 Spin-orbit coupling
Oxo-process 1614 Roussin's salt 1371
splitting 1158, 1165
Oxomercuration 1428 Square planar-tetrahedral
th
,Oxophilicity 1517, 1526 equilibrium of Ni(II) and

Co(l'I) 1202
e/
Saddle point 1605, 1607 SQUID 1116

Sandwich compound 1298, 1454, Stereochemical nonrigidity 1152,
t.m
1476, 1479, 1481, 1487 1554

1t-Acid ligands 1354 Schlenk equilibrium 1409 Stereochemically active
Paramagnetic substance 1097 Schrock carbenes 1513 lone pair 1424
Scientific serendipity 1297, 1463 Stereoregularity of polymers 1629
e
Paramagnetism and thermal

energy 1120 Scrambling of Me-groups in Strictly orthogonal 1238
er
Pascal's constants 1106 Al2Me6 1550 Substitution of CO group 1508

Pentadienyl group 1458 Scrambling of the bridging and Substitution reactions of the
H
Permeability 1088 terminal carbonyls 1565 carbonyl complexes 1503

Phosphines 1382 Scrambling reactions 1425, 1550 Sulfur dioxide (:S02) as a 1t-acid
k
Phosphites 1382 Second order Zeeman effect 1135 ligand 1381

Serendipity 1296, 1297, 1463 Superexchange in CU202 ring 1239
lic
Photocatalyst (Ti0 2) 1642

Pole strength 1087 Sigma-bond metathesis 1549 Superexchange interaction in the
Polyhedral skeletal electron pair Sigma-bonded Cr202 ring 1238
C
theory (PSPT) 1348 organometallics 1432, 1433 Superexchan'ge phenomenon 1206,

Polymerisation catalyst 1419 Silazenes 1421 1212
Polymerisation of olefins 1629 Silene complexes 1445 Syndiotactic polymer 1629
Polynuclear carbonyls 1301, 1342 Silicones 1421 Synergistic 0- and
Polyolefins 1439 Smidt reaction 1624- 1t-bonding 1323, 1437
Polytopal rearrangement 1552, SNG 1640 Synthesis gas 1636
1557 Spin frustrated system 1260 Synthetic gasoline 1638-1640
Pseudosubstitution 1577 Spin state isomerism in the Synthetic natural gas (SNG) 1636,
PSPT theory 1348 octahedral complexes 1182 1640
Push-pull mechanism 1416, 1417 Spin cross-over 1176 Synthetic petrol 1636
SUBJECT INDEX 1.5
Water gas shift reaction

(WGSR) 1316, 1351, 1636
Tautomeric structures 1310 Uranocene 1487 Weak ferromagnetism 1257
Tebbe's reagent 1517 Weiss constant 1099
Temperature independent para- Wilkinson's catalyst 1608
magnetism (TIP) 1100, 1127 Wittig reaction 1517
Template synthesis 1578
ry
Terminal CO group 1311 Van-Vleck Equation 1126, 1283,
Thermochromism 1204 1288
ra
Tolman's cone angle 1383 Vaska's complex 1317, 1375,
Transition metal oxides 1255 1398, 1439, 1532, 1536, Zeeman effect 1127
ib
Transmetallation 1427, 1428 1608 Zeise's salt 1296, 1437
Triangular trinuclear Vitamin B 12 1297 Zero-point energies 1176
yl
complexes 1293 Ziegler catalyst 1629, 1630
m
Tropylium cation 1484 Ziegler -Natta catalyst 1419,
Turnover number 1606 1629, 1630
he
Turnstile rotation 1556 Zinc alkyls 1425
Twisting mechanism 1557 Wacker process 1624 ZSM-5 catalyst 1638
lc
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th
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Asim K. Das Vol 6 The Alchemy Library

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Asim K. Das Vol 6 The Alchemy Library

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C

J.T. Distortion; Spectrochemical Series; Stabilities of Complexes.

Metal··€omplexes - Reaction Mechanisms (Ligand Substitution, Isomerisation,

Magnetochemistry and Magnetic Properties of Metal Complexes; Struct.ure,

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Reprint: 2015, 2016

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included. Magnetochemistry and organometallic chemistry have been covered. Applications

the goddess of learning.

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8.8 Comparison of the Properties of Different Types of Magnetic Substances 1101

8.9 Sources of Paramagnetism and Magnetic Properties of an Electron 1101

8.10 Origin of Diamagnetism and Lorenz's Law 1103

Balance Method 1109

8.14 Paramagnetism and Thermal Energy 1120

Zeeman Effect 1135

Complexes; Spin-State Isomerism in the Five Coordinate Complexes

Involving an Intermediate Spin

Octahedral - Square Planar Equilibria for the Nickel(II) Complexes; Monomer-Polymer

Kanamori-Anderson Rules (GKA Rules) 1206

8.30 Antiferromagnetism in the Magnetically Concentrated Systems: Pathways of

8.34 Competing Interactions and Spin Frustation 1258

Interacting Spins in a Tetrahedral Arrangement: A Spin Frusted System ; Examples

...nrJMetal Carbonyls: n-Acid Metal Complexes:

9.1 Introduction and Important Milestones of Historical Importance 1295

(M-C) Bonds; Important Milestones in the Development of Organometallics

9.11 Chemistry of Dinitrogen Complexes: Activation of Dinitrogen 1386

9.13 Chemistry of Dioxygen Complexes: Activation of Dioxygen 1391

Elements; Preparation and Properties of the Organometallics of Group 12 Elements

Carbenes and Carbynes 1430

Stabilising the Sigma-Bonded Organometallics; Synthesis of the Sigma-Bonded

9.19 Allyl Complexes 1452

10.4 Metal Carbonyls as Nucleophiles and Bronsted Bases 1518

Characteristics of CO Insertion: Carbonylation and Decarbonylation Reactions; Olefin

General Aspects of Oxidative Addition; Scope of the Oxidative Addition Reaction;

10.7 Reductive Elimination 1543

10.8 Activation of C-H Bonds Through the Oxidative Addition 1545

10.9 C-H Bond Activation through THE Sigma-Bond Metathesis 1549

10.14 Photochemical Reactions: Photocatalyst (Ti0 2) 1642

Appendix I: Units and Conversion Factors A-I

Appendix III: Wavelength and Colours A-4

Appendix VI: Books Consulted A-9

Subject Index 1-1-1-5

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(Note: In SI system, for r = I meter (in air), ml = m2 = I,

I = m = ml ,A = area, 1 = distance between the poles.

(a) Diamagnetism (b) Paramagnetism (c) Ferromagnetism

In air, B = JloH, (in SI unit).

J.lo H m- 1 or T m A-I (SI system)

dimension of gauss. Taking B = 1 gauss, i.e. 10-4 T, we have:

Xg = k, p = density of the substance

XM (molar susceptibility) = XgM (M = molecular mass of the substance).

_m_ = - - - , where Jlm = magnetic moment per molecule

VM = molar volume; I = magnetic moment per unit volume.

molar magnetic moment N Jl

field strength) (ampere per meter) as gauss)

permeability) (henry per meter)