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ESSENTIALS OF
COORDINATION
CHEMISTRY
A Simplified Approach
with 3D Visuals
VASISHTA BHATT
UGC-Human Resource Development Centre
Sardar Patel University
Vallabh Vidyanagar, Gujarat, India
Amsterdam • Boston • Heidelberg • London

New York • Oxford • Paris • San Diego
San Francisco • Singapore • Sydney • Tokyo
Academic Press is an imprint of Elsevier
Academic Press is an imprint of Elsevier
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525 B Street, Suite 1800, San Diego, CA 92101-4495, USA
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The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK
Copyright © 2016 Elsevier Inc. All rights reserved.
No part of this publication may be reproduced or transmitted in any form or by any

means, electronic or mechanical, including photocopying, recording, or any information
storage and retrieval system, without permission in writing from the publisher. Details on
how to seek permission, further information about the Publisher’s permissions policies
and our arrangements with organizations such as the Copyright Clearance Center and the
Copyright Licensing Agency, can be found at our website: www.elsevier.com/
permissions.
This book and the individual contributions contained in it are protected under copyright
by the Publisher (other than as may be noted herein).
Notices
Knowledge and best practice in this field are constantly changing. As new research and
experience broaden our understanding, changes in research methods, professional
practices, or medical treatment may become necessary.
Practitioners and researchers must always rely on their own experience and knowledge in
evaluating and using any information, methods, compounds, or experiments described
herein. In using such information or methods they should be mindful of their own safety
and the safety of others, including parties for whom they have a professional
responsibility.
To the fullest extent of the law, neither the Publisher nor the authors, contributors, or
editors, assume any liability for any injury and/or damage to persons or property as a
matter of products liability, negligence or otherwise, or from any use or operation of any
methods, products, instructions, or ideas contained in the material herein.
ISBN: 978-0-12-803895-6
Library of Congress Cataloging-in-Publication Data

A catalogue record for this book is available from the Library of Congress
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library
For information on all Academic Press publications

visit our website at http://store.elsevier.com/
To the teachers and learners of coordination chemistry
PREFACE
This book is an outcome of my research programmes, coupled with

teaching about 10,000 learners over a period of two decades. While
teaching, I realized that students perceive chemistry as one of the most
difficult subjects. On pondering over the reason, I came to a conclusion that
teachers find it difficult to make the students imagine the structures of
atoms, ions and molecules as they are to be understood. As a result, many
chemistry classrooms lack the desired resonance. The obvious remedy was
to create the images and movies that describe these species to a maximum
extent. I have been trying to achieve this end for some time now. I realized
that there is still more to be done to make chemistry simple enough for
students.
Apart from this, there are other constraints faced by chemistry teachers
as well, which require attention. Often, professors face time constraints in
discussing the intricacies of certain concepts in the classroom. Hence, it
becomes a ‘fixed placeefixed time’ mode of education. In this age, when
knowledge could transcend the borders of time, place and community, an
all timeseall places mode of learning was, therefore, an inevitable way out.
This book is an outcome of the above rationale.
As it is said, a book is a person’s best friend. Even more so, if it offers
self-learning facilities with features like numerous images and videos of
good quality, clear illustrations and relevant citations, as well as lucid
language.
Essentials of Coordination Chemistry: Simplified Approach with 3D Visuals is
a step in the direction of developing a lifelong friendship between the book
and the learner. It includes subject matter for an entire semester in the
course of BS/BSc with chemistry as a major. It begins with basic coordi-
nation chemistry and basic concepts of symmetry, which serve as a primer
for advanced learning. A detailed discussion on isomerism amongst coor-
dination compounds is provided in the subsequent chapter. The next three
chapters cover classical topics related to the thermodynamics and kinetics of
complex formation, as well as a variety of reactions occurring in coordi-
nation compounds of square planar and octahedral geometry. In the last
section of the book, beginning with basic organometallic chemistry, a brief
discussion on general organometallic chemistry is provided, which is then
extended particularly to an industrially important class of organometallic
complexes: metal carbonyls and metal nitrosyls. The electronic version of
xi
xii Preface
this is expected to be a camera-ready set of lectures that can be readily

delivered in the class. Moreover, at the end of every chapter, some exercises
based on the text are also provided. An attempt has been made to include
the latest developments in the subject. For instance, brief information on
the HoveydaeGrubbs’ catalyst or the Suzuki reaction, as well as others
from the twenty-first century, is included in this book. I hope that this
book will cater to the needs of the students and teachers.
I am indeed keen to receive constructive comments and suggestions
from the teachers’ and learners’ fraternity for potential improvisations in
this book.
Vasishta Bhatt
ACKNOWLEDGEMENTS
First of all, I must thank Elsevier Inc. for putting trust in my ability to
complete this work. I thank Cathleen Sether (Publishing Director), Katey
Birtcher (Senior Acquisitions Editor, Chemistry), Jill Cetel (Senior Editorial
Project Manager) and the entire Elsevier team for making this dream
journey a reality.
I sincerely acknowledge the support of the University Grants Com-
mission (UGC), New Delhi, India, for giving me an office and a position
from which I could comfortably complete this book; it would have been
impossible otherwise. The Vice Chancellor of Sardar Patel University,
Dr Harish Padh, has remained a prime source of my inspiration, as he is a
role-model scientist anyone would want to emulate. Dr A.R. Jani, the
Director of UGC-Human Resource Development Centre at Sardar Patel
University, was very happy when I took this assignment, and he readily
arranged for all the facilities that would make me comfortable in preparing
this book. He also provided vital scientific guidance. My fellow colleague,
Mr Vimal Shah, needs to be acknowledged for his valuable suggestions; as a
layman, it really helped me in predicting the learner’s perspective on
technical issues. The entire staff of my institute whole heartedly supported
me in this endeavour. Prof. Mangala Sunder Krishnan, IITM Chennai and
National Coordinator of the NPTEL, has remained the torch bearer in this
entire journey. The faculty members of the chemistry department of Sardar
Patel University, namely Prof. M.N. Patel, Prof. N.V. Sastry and Prof. D.K.
Raval, strongly encouraged me and offered all the guidance that I desired.
How can I forget the assistance provided by Mr Ravish Patel, who worked
as my assistant and helped me on each and every step!
My family remained the main driving force behind this project. I could
never have completed this book if they were not there. Sonal (my wife) and
Ishan (my son) contributed in all possible manners, beginning with the
sacrifice of their vacation outings. Both of them gave creative criticism and
suggestions on many pedagogical issues whenever I was in doubt. Mothers
and fathers are the first teachers of a child; Ramaben and Dineshbhai will be
the happiest people on the earth when this book takes its final form.
All the teachers and learners of coordination chemistry have knowingly
or unknowingly contributed a lot to this work. This book is now to be
tested for their expectations.
Vasishta Bhatt
xiii
CHAPTER 1
Basic Coordination Chemistry

Contents
1. Introduction 1
1.1 Definitions 3
2. Nomenclature 9
2.1 For Writing the Coordination Formula 9
2.2 For Writing the Names 10
3. Theories of Bonding in Coordination Compounds 12
4. Geometries of Complexes with Different Coordination Numbers 13
5. Crystal Field Theory 20
5.1 Ligand Field Theory (LFT) 20
6. Splitting of d-Orbitals in Fields of Different Geometry 20
6.1 Ligand Field Stabilization Energy (LFSE) 23
6.1.1 Tetragonal Distortions in an Octahedral Field 24
6.1.2 The Molecular Orbital Theory 24
7. Magnetism 27
7.1 Diamagnetism 28
7.2 Paramagnetism 28
7.3 Ferromagnetism and Antiferromagnetism 28
7.4 The Spectrochemical Series 30
8. Catalytic Properties 31
9. Exercises 34
9.1 Multiple Choice Questions 34
9.2 Short/Long Answer Questions 34
Suggested Further Readings 35
References 35
1. INTRODUCTION
The coordination compounds found their applications long before the
establishment of coordination chemistry. Bright red coloured alizarin dyes
were under applications even before the fifteenth century. This bright red
dye, now characterized as a chelated complex of hydroxyanthraquinone
with calcium and aluminium metal ions, is shown in Figure 1.
Later, in the sixteenth century, the formation of a well-known member
of today’s coordination chemistry family, the tetraamminecupric ion
Essentials of Coordination Chemistry © 2016 Elsevier Inc.

http://dx.doi.org/10.1016/B978-0-12-803895-6.00001-X All rights reserved. 1
2 Essentials of Coordination Chemistry
Figure 1 Structure of alizarin dye.
[Cu(NH3)4]þ2, was recorded upon contact between brass alloy and

ammonium chloride. Addition of Prussian blue Fe4[Fe(CN)6]3$xH2O
increased the use of coordination compounds in dyes and pigments. A
platinum complex K2[PtCl6] offered an application for the refinement of
platinum metal. Thus, before the coordination chemistry was structured,
the coordination compounds, complexes and chelates found their
applications.
A systematic investigation of structure and bonding in coordination
chemistry began with the inquisitiveness of Tassaert (1798), which was
extended by distinguished chemists like Wilhelm Blomstrand, Jorgensen
and Alfred Werner [1] until the end of the nineteenth century. In the
events, Werner’s coordination theory (1893) became the base of the
modern coordination chemistry. It is worth noting that the electron was
discovered subsequent to Werner’s theory.
The bonding in compounds like CoCl3 and NH3 were easily under-
stood and explained and hence such compounds were regarded as simple
compounds. For instance, the þ3 formal oxidation of cobalt in cobalt
chloride is balanced by three uni-negative chloride ions and the coexistence
of these ionic moieties to form a molecule is understood and explained.
Similarly, the valence shell (n ¼ 2) of nitrogen (N ¼ 7) contains five
electrons and four orbitals (2s, 2px, 2py and 2pz). Keeping an electron pair
Basic Coordination Chemistry 3
in one of these orbitals while the other three remains half filled, an op-
portunity for three hydrogen atoms to contribute one electron each for the
formation of a covalent bond with nitrogen, can also be explained. Thus an
ammonia molecule has three NeH covalent bonds and one lone pair of
electrons over the nitrogen atom. It is worth noticing here that all the
valencies of all the atoms in both the molecules are fully satisfied and hence
there is no further scope of bonding.
A ‘complex’ situation arises when one comes to know that the molecule
CoCl3 can encompass six ammonia molecules, resulting into a third in-
dependent entity. This situation was fully understood and explained by
Werner’s coordination theory, followed by naming the entity as ‘complex’.
1.1 Definitions
Coordination compounds are the compounds containing one or more
coordinate covalent bonds.
Coordinate covalent bonds are the covalent bonds in which both the
bonding electrons are contributed by one of the bond partners. Figure 2
distinguishes the covalent bonds from the coordinate covalent bond in
NH3BF3. While the three BeF covalent bonds are formed due to the
sharing of electron pairs resulting from contributions of both boron and
fluorine atoms, an NeB bond is formed due to the donation of a lone pair
Figure 2 Bonding in NH3BF3.

of electrons from nitrogen into the empty orbitals of boron. The coordinate
covalent bond is shown by an arrow with its head pointing towards the
direction of the donation of an electron pair, as shown in Figure 2.
A complex is a molecule/ion containing a central metal atom/ion
surrounded by a definite number of ligands held by secondary valences or
coordinate covalent bonds.
Primary valency refers to the charge over the metal ion e.g. Co(III)
has þ3 charge, which can be balanced by 3 charge-forming compounds
like CoCl3. The primary valency is ionic and is satisfied in the second
coordination sphere, as shown in Figure 3.
Secondary valency is the number of empty valence orbitals, as illus-
trated for [Co(NH3)6]Cl3 in the figure. The Co(III) ion has six empty
valence orbitals. Hence its secondary valency is six. Secondary valency is a
coordinate covalent valency, and it is satisfied in the first coordination
sphere of the metal ion, as shown in Figure 4.
Coordination number is a property of the metal ion representing the
total number of donor atoms directly attached to the central atom. In the
above case, the coordination number of Co(III) is six, as six nitrogen donor
atoms are directly connected to the central metal ion (cobalt(III)).
Ligand is any atom, ion or neutral molecule capable of donating an
electron pair and bonded to the central metal ion or atom through sec-
ondary valency.
Figure 3 First and second coordination spheres in [Co(NH3)6]Cl3.

Figure 4 Secondary valency of Co(III) in [Co(NH3)6]Cl3.
Dentate character is a property of a ligand representing a number of

coordinating atoms.
In the case of [Co(NH3)6]Cl3, ammonia, NH3 the ligand contains one
donor atom (N). Hence its dentate character is one and is classified as a
monodentate ligand. Similarly, chloro (Cl) is an anionic, monoatomic and
monodentate ligand, while hydroxo (OH) is a diatomic, monodentate and
anionic ligand. Aquo (OH2) represents a neutral triatomic monodentate
ligand. A few popular ligands and their characteristics are shown in
Figure 5.
Due to a higher dentate character of ligands, a variety of complexes
known as chelate is also formed sometimes. Chelate is a compound formed
when a polydentate ligand uses more than one of its coordinating atoms to
form a closed-ring structure, which includes the central metal ion. Five-
and six-membered rings are known to provide extra stability to the chelates.
The process of chelate formation is known as chelation. A polydentate
ligand involved in chelate formation is also known as a chelating ligand.
Chelates generally exhibit higher stability than analogous complexes.
A polydentate ligand may be attached to the central metal ion through
more than one kind of functional group. The number and kind of linkages
by which the metal ion is attached with the ligands can thus become a
criterion for the classification of chelates. The covalent bonds are formed by
the replacement of one or more H-atoms, while coordinate covalent bonds
are formed by the donation of an electron pair from the ligands. Some of
the chelates involving a variety of polydentate ligands and linkages are
shown in Figure 6. The coordinate covalent linkages are shown by thin,
thread-like bonds.
Ethylenediamine (en), neutral, bidentate
Acetyleacetone (acac), neutral, bidentate
2-hydroxylbenzaldehyde also known as

salicylaldehyde (sal), anionic, bidentate
Dimethylglyoxime(dmg), anionic, bidentate
2,2′-bipyridine, neutral, bidentate
Figure 5 Structures and characteristics of a few important ligands.

H
H
H H
N H
C C C H Diethelenetrimine (dien), neutral, terdentate
N H
H C
H H H
H N
H
Nitrilotriacetic (nta), anionic, quadridentate
2,2ʹ,2ʹʹ-triaminotriethylamine (tren), neutral,

quadridentate
H C
O C O
O C N
C C Ethylenediaminetetraaceticacid (edta),
N C H
C C O anionic, sexadentate
H O O
C C H
O
Figure 5 Cont'd
EXAMPLE CHARACTERISTICS
Oxalic acid
Anionic
Bidentate
Two covalent bonds
Two five-membered rings in the chelate
Glycine
Anionic
Bidentate
One covalent and one coordinate
covalent bond
1,10-phenanthroline
Neutral
Bidentate
Two coordinate covalent bonds
1,2,3-trihydroxypropyl hydrogen carbonate

Anionic
Tridentate
Three covalent bonds
Two five-membered rings and one
six-membered ring in the chelate
2-aminosuccinic acid also known as

aspartic acid
Anionic
Tridentate
Two covalent and one coordinate
covalent bond
Two five-membered rings, two six-membered
rings and two seven memebered
rings in the chelate
Figure 6 Structures and characteristics of a few chelates.

1,2,3-triaminopropane
Neutral
Tridentate
Three coordinate covalent bonds
Four five-membered rings and two
six-membered rings in the chelate
2,3-diaminopropanoicacid
Anionic
Tridentate
One covalent and two coordinate
covalent bonds
Four five-membered rings and two
six-membered rings in the chelate
Figure 6 Cont'd
Polynuclear complex is a complex with more than one metal atom/

ion. These metal ions are sometimes bridged through appropriate ligands,
resulting into the formation of a bridged polynuclear complex.
2. NOMENCLATURE
A systematic nomenclature of coordination compounds requires a careful
consideration of the following rules [2]. The learner should first learn all of
these rules by heart and then do sufficient practice to master the procedure.
2.1 For Writing the Coordination Formula

1. Place the symbol of the central atom first followed by the symbol of the
ligand in the following order: anionic, neutral and cationic. Enclose the
complex in a square bracket.
2. If the formula of a charged complex is written without any counter-ion,
the charge is to be indicated outside the square bracket as a right super-
script with the number preceding the sign, as in [PtCl6]2 or
[Cr(OH2)6]3þ; the oxidation number of a central atom/ion may be
optionally represented by a Roman numeral placed as a right superscript
on the element symbol, as in [CrIIICl3(OH2)3] and [FeII(CO)4]2.
Figure 7 trans-[CoIIICl2(sal)(en)].
3. The anionic ligands are cited first and in alphabetical order, according to
the first symbols of their formulae.
4. The neutral and cationic ligands are then listed in the following order:
H2O, NH3, other inorganic ligands and organic ligands in alphabetical
order.
5. The structural information may be given by prefixes such as cis-, trans-,
fac-, mer- etc.
To illustrate the above rules, consider the writing of a coordination
formula for the compound shown in Figure 7 as trans-[CoIIICl2(sal)(en)].
N.B.: The ligand abbreviations and the formulae of the polyatomic
ligands are generally placed in parentheses.
2.2 For Writing the Names

1. The cation is named first, followed by the name of the anion irrespec-
tive of whether the cation or the anion is the complex species.
2. In a complex (cationic, anionic or neutral), the names of the ligand are

cited alphabetically irrespective of their charge without separation, and
the name of the central metal atom is the last.
3. The names of the anionic complexes have the specific ending ‘-ate’ or
‘-ic’ (if named as acid), while there is no such specific ending of cationic
or neutral complexes.
4. The oxidation state of the central atom is indicated by a Roman
numeral in the parenthesis at the end of the name of the complex.
5. Name of the ligands: the specific ending ‘-o’ is given to organic/
inorganic anionic ligands. In the case of ligand names ending in
‘-ide’, ‘-ite’ or ‘-ate’, ‘e’ is replaced by ‘o’, giving ‘-ido’, ‘-ito’ or
‘-ato’ respectively, as in -azide ðN3 Þ becomes azido, -nitrite
ðNO3 Þ becomes nitrito and -sulphate ðSO4 2 Þ becomes sulfato.
However, certain anionic ligands are exceptions to the above rule
and are named as shown in Table 1.
There is no change in the name of neutral ligands. They are named
as a molecule as in NH2CH2CH2NH2 (en) as ethylenediamine and
NH2CH2CH2NH CH2CH2NH2 (dien) as diethylenetriamine. Here
also, the exceptions are H2O (named as aquo), NH3 (as ammine),
NO (as nitrosyl) and CO (as carbonyl) etc.
The cationic ligands have the specific ending ‘ium’, as in
NH2 eNH3 þ , named as hydrazinium, and H2 NeCH2 eCH2 eNH3 þ ,
named as 2-aminoethylammonium.
6. The number of each kind of simple ligand is indicated by prefixes such as
mono-for one ligand, which is usually omitted, di- for two ligands and tri-
for three ligands without any space. In the case of complicated ligands, the
prefixes bis- for two ligands, tris- for three ligands and tetrakis- for four li-
gands (with the name of the ligand enclosed in parenthesis) is used.
7. The coordinating atom of a ligand to the central atom is indicated by
placing the symbol k (Kappa) followed by the elemental symbol after
Table 1 Names used for anionic ligands according to International Union of Pure
and Applied Chemistry (IUPAC) nomenclature
Ligand Name Ligand Name Ligand Name
F Fluoro OH Hydroxo O2 2 Peroxo
Cl Chloro CN Cyano CH3O Methoxo
Br Bromo HS Thiolo C5 H5 Cyclopentadienyl
I Iodo S2 Thio C6 H5 Phenyl
H Hydrido O2 Superoxo O2 Oxo
the name of the ligand, as in M-SCN-, it is written as thiocyanato-kS

and in M-NCS-, it is written as iosthiocynato-kN.
8. A ligand that bridges two central atoms is designated by the symbol m
before its name.
Here are a few examples of using IUPAC nomenclature for writing
the formulae and names of coordination complexes.
Formula Name
4
[Fe(CN)6] Hexacyanoferrate(II) ion
[CoCl3(NH3)4] Triamminetrichlorocobalt(III)
[CuCl2(CH3NH2)2] Dichlorobis(methylamine)copper(II)
Cis-[PtCl2(NH3)2] Cis-diamminedichloroplatinum(II)
[PtCl(en)NH2NH3]þ2 Chloroethylenediaminehydraziniumplatinum(II)
ion
[Fe(CN)(CNCH2C6H5)5]þ Pentakis(benzylisocynide)cyano iron(III) ion
[Al(OH)(H2O)5]þ2 Pentaaquohydroxoaluminum(III) ion
[Co(CN)(CO)2NO] Dicarbonylcyanonitrosylcobaltate(0) ion
[PtClNO3(NH3)2(en)]SO4 Diammine(ethylenediamine)
chloronitroplatinum(IV) sulphate
K[SbCl5(C6H5)] Potassium pentachloro(phenyl) antimonite(V)
H2[PtCl6] Hexachloroplatinic(IV) acid
Na2[Fe(CN)5NO] Sodium pentacyanonitrosylferrate(III)
[PtPy4][PtCl4] Tetrakis(pyridine)platinum(II)
tetrachloroplatinate(II)
[Pt(NH3)4Br2]Br2 Tetramminedibromoplatinum(IV) bromide
3. THEORIES OF BONDING IN COORDINATION

COMPOUNDS
The theories of bonding in coordination compounds [3] have evolved sub-
sequent to Werner’s coordination theory (1893). Werner introduced the
concept of primary and secondary valency, explaining the formation of the
coordination compounds. The 18-electron rule, stating that the stable com-
plexes with low formal oxidation states of metal ions should have 18 bonding
electrons around the metal ion, became an important beginning point toward
the study of the stability of the complexes. The 18-electron rule is significant
in modern coordination chemistry as it is also supported by the molecular
orbital theory. However, a smaller number of complexes with metals in low
oxidation states restrict its wide applicability. An important advance in the
theories of bonding in coordination compounds was the introduction of
Figure 8 Covalent and coordinate covalent bonding in BF3NH3.
valence bond theory (VBT), which is actually an extension of Lewis theory

(1902) and Heitler–London theory (1927). From the above two theories, the
sharing of electron pairs by atoms and the formation of bonds was understood
and explained. The VBT developed by Linus Pauling introduced two key
concepts in the theories of bonding, viz, the hybridization of orbitals and
resonance, the absence of which were the drawbacks of the previous theories.
According to this theory, the metal ions are regarded as Lewis acids
characterized by the availability of low lying, empty orbitals suitable for
accommodating the accepted electrons. The ligands are the Lewis bases,
characterized by the availability of a lone pair of electrons that can be
readily donated, resulting into a formation of a coordinate covalent bond.
Thus, the acid–base characteristics of metal and ligand complement each
other to give rise to a coordinate covalent bond, as shown in Figure 8.
Hybridization of atomic orbitals, a mathematical tool for mixing the
atomic orbitals to give an equal number of hybrid orbitals with superior
directional properties, became a very important feature of this theory in
explaining various geometries observed in coordination compounds.
4. GEOMETRIES OF COMPLEXES WITH DIFFERENT

COORDINATION NUMBERS
1. Coordination number 2: This is a relatively uncommon coordination
number and is restricted to a few cases, such as Cu(I), Ag(I), Au(I), and
Hg(II) ions having d10 configuration. [CuCl2] and [Ag(NH3)2]þ are
the representative complexes of this coordination number.
The possible geometries for the complexes with CN ¼ 2 are linear
and angular. Linear geometry is commonly observed in such complexes,
as it involves minimum ligand–ligand repulsion. These complexes

involve sd-hybridization between the central metal atom orbitals, as
shown in Figure 9.
Orgel has suggested that (n1)d orbitals have nearly the same energy
as that of ns and np orbitals. The dz2 orbitals can enter into this hybrid-
ization to remove electron density away from the region of ligands and
stabilize the complex. Initially ‘4s’ and ‘3dz2 ’ orbitals hybridize to give
two sd-hybrid orbitals, namely j1 and j2. The j2 sd-orbitals have their
positive lobes along the z axis, while the j1 is in the XY plane. The j2
orbitals, further hybridized with pz orbitals, give the hybrid orbitals
concentrated along the z-direction. The electron pair from the dz2
orbitals now occupy the sd orbital XY plane, while hybrid orbitals
concentrated along the z-direction are available for a stronger bond
along the z axis, resulting into a complex with linear geometry.
Figure 9 Hybridization explaining the bonding in [CuCl2].

The chelates of this coordination number are less stable than analo-
gous complexes. Consider the complexes [Ag(en)]þ and [(Ag(NH3)2]þ.
In these complexes, the favoured geometry is linear. In [Ag(en)]þ
chelate, a five-membered ring is formed, and the ‘en’ molecule cannot
occupy linear coordination positions around Agþ without introducing
strain in the chelate ring, which destabilizes the complex. Hence
[Ag(en)]þ is less stable than [(Ag(NH3)2]þ. The Ag(I) chelates with
six-, seven- or eight-membered rings are more stable; as in larger-
sized chelate rings, the strain is less, hence stability is greater.
2. Coordination number 3: This is very rare coordination number. In
most cases, detailed studies have shown a higher coordination number
attained by the central metal atom through dimerization and bridging,
as in the cases of AlCl3 and PtCl2(PR3), shown in Figure 10.
However, CN ¼ 3 is also illustrated by a few true complexes such as
HgI3 and [Cu(SPMe3)] ions. These complexes exhibit trigonal planar
geometry, as shown in the figure.
3. Coordination number 4: This is one of the most commonly observed
coordination numbers. There are two possible geometries associated
with CN ¼ 4, viz, tetrahedral and square planar.
a. Tetrahedral complexes: Tetrahedral geometry is fairly common
in four-coordinate complexes of nontransition metal ions. This ge-
ometry involves sp3 hybridization of orbitals of the central atom.
This geometry is favoured by large ligands like Cl, Br, I and
small metal ions like Beþ2 and Alþ3. Complexes like [BeF4]2,
[ZnCl4]2 and Be(acac)2, shown in Figure 11, illustrate the tetrahe-
dral complexes with CN ¼ 4.
b. Square planar complexes: Square planar coordination is less fav-
oured structurally (due to stronger ligand–ligand repulsion) than
tetrahedral coordination, especially by large ligands. If the ligands
are small, octahedral coordination can be achieved. Few metal
ions are known to form square planar complexes; it is mostly
restricted to d8 to d9 ions like Pt(II), Pd(II), Ni(II), Cu(II) and
Au(II), as illustrated in [Pt(NH3)4]2þ, [PtCl2(NH3)2] and
[Ni(CN)4]2 shown in Figure 12.
4. Coordination number 5: The two possible geometries for this coor-
dination number are trigonal bipyramidal (TBP) and square pyramidal
(SqPy). In most cases, the structure is found to be distorted. The con-
version between these two geometries can easily occur by slight
Figure 10 Dimerization and bridging in (a) AlCl3 (b) PtCl2P(CH3) and (c) [Cu(SPMe3)].
Figure 11 Tetrahedral Be(acac)2 chelate.
Figure 12 Square planar [Ni(CN)4]2 complex ion.
deformation. However, [CuCl5]3 and [NiCN5]3 exhibit TBP and

square pyramidal geometry respectively, as shown in Figure 13.
5. Coordination number 6: This is the most common coordination
number. Some metals like Cr(III) and Co(III) almost exclusively form
six-coordinate complexes. There are three popular arrangements of
six ligands around the central metal ion, viz, hexagonal planar, trigonal
prismatic and octahedral, as shown in Figure 14.
Figure 13 (a) Trigonal bipyramidal [CuCl5]3 and (b) Square pyramidal [NiCN5]3 ions.
Figure 14 (a) Hexagonal planar, (b) trigonal prismatic and (c) octahedral geometries.
An extensive structural study of the complexes with CN ¼ 6 has shown

that the arrangement of six ligands in a six-coordination compound is al-
ways octahedral. In octahedral complexes, d2sp3 or sp3d2 hybridization of
orbitals is observed. Perfect octahedral symmetry can be observed only
when all of the six ligands are identical, otherwise the geometry gets dis-
torted. It may show either tetragonal or trigonal distortion, as shown in
Figure 15.
Complexes with higher coordination numbers have also been reported,
but considering the scope of the book, the discussion on such complexes is
knowingly omitted.
Though VBT has remained a necessary tool for the study of metal
complexes, it is not sufficient to explain the colour and characteristics of the
absorption spectra of the complexes. The theory could not demystify the
Figure 15 Distortions in octahedra.

mystery of the formation of outer and inner orbital complexes. The dis-
tortions in the shapes of the coordination complexes from regular geometry
were outside the purview of the VBT. Moreover, orbital contributions and
temperature dependency on magnetic moment of coordination complex
are not properly explained by VBT.
5. CRYSTAL FIELD THEORY

Bethe and Van Vleck developed the crystal field theory (CFT) [4] for
coordination in the early 1930s. CFT treats the coordination compounds as
simple ionic compounds. The bonding in coordination compounds is due
to electrostatic forces between the positively charged metal ions and the
negatively charged ligands and, in the case of neutral ligands, dipoles. This
theory fits well for complexes of metal ions with small and highly elec-
tronegative ligands, such as F, Cl and OH2, but it does not work well
with ligands having less polarity, such as carbon monoxide. CFT also needs
modification to explain the difference between the spectra of free metal
ions from the complexed ones. Considering the simplicity of the CFT and
the complexity of the bonding in complexes, the CFT is regarded as a
theory that is too good to be true.
5.1 Ligand Field Theory (LFT)

The first article on Ligand Field Theory (LFT) [5] was authored by Orgel
and Griffith in 1957. The LFT considers the contributions from both ionic
and covalent bonding for accounting the properties of coordination com-
pounds. The LFT is a combination of molecular orbital (MO) theory and
CFT. The transition metals form a large number of complexes: they formed
coloured ions, they form paramagnetic compounds, they show variable
oxidation states and they also exhibit catalytic activity. All these properties
can only be explained by studying their electronic structures, spectra and
magnetic properties. LFT is a term that is used to describe the whole toolkit
required to understand the bonding and other properties of the transition
metal elements and their compounds.
6. SPLITTING OF d-ORBITALS IN FIELDS OF DIFFERENT

GEOMETRY
The fivefold degenerate d-orbitals are shown in Figure 16. They are
designated as dxy, dyz, dxz, dx2 y2 and dz2 . The lobes of dxy, dyz and dxz
Figure 16 Shapes of five d-orbitals.
orbitals lie in the xy, yz and xz planes, respectively. These lobes do not
touch any of the axes. These orbitals are known as a t2g set of orbitals. The
lobes of dx2 y2 and dz2 lie on the x and y axes and z axis, respectively. These
orbitals are known as an eg group of orbitals.
Figure 17 shows the nucleus of a transition metal ion coinciding the
origin (0,0,0) of a Cartesian coordinate system. The five d-orbitals of the
ion are thus extending from the origin of the Cartesian coordinate system.
Consider six uni-negative monodentate ligands slowly approaching the
central metal ion, as indicated by negative point charges. The ligands are
approaching along the x, y and z axes, forming an octahedral field. As
the ligands come closer to the nucleus of the metal ion, they encounter
the orbitals of the metal ion. Thus there will be repulsion between the
orbital (they contain electrons) and the ligands (they are negatively
charged). The eg orbitals that are oriented along the axes face the stronger
repulsion, as compared to that of the t2g orbitals lying in the plane. Due to
this, the degeneracy of the fivefold d-orbitals split into t2g orbitals with
lower energy and eg orbitals with higher energy, as shown in the left part
of Figure 18.
The magnitude of the splitting of d-orbitals due to the introduction of
an octahedral ligand field is Do, where 3=5 Do is the extent of increase in
energy of eg orbitals and 2=5 Do is the corresponding decrease in energy of
t2g orbitals, as compared to the energy for the free metal ion.
Figure 17 A metal ion coincident with the origin of a Cartesian coordinate system.
Figure 18 Splitting of d-orbitals in octahedral and tetrahedral fields.

Introduction of a tetrahedral ligand field can be visualized by coinciding

the centre of a cube with the origin of the Cartesian coordinate system. The
four monodentate ligands in a tetrahedral complex approach the nucleus of
the metal ion through the alternate diagonals of the opposite faces of the
cube. Thus these ligands approach the metal ion along the planes xy, yz and
xz. This results into an increase in repulsion in t2g orbitals and, in turn, the
increase in energy of t2g orbitals and corresponding decrease in the energy
of eg orbitals, as shown in the right part of Figure 18.
The magnitude of the splitting of d-orbitals due to introduction of a
tetrahedral ligand field is Dt, where 2=5 Dt is the increase in energy of t2g
orbitals, while 3=5 Dt is the corresponding decrease in energy of eg orbitals,
as compared to the energy for the free metal ion.
If the ions and interionic distances are the same, an empirical relation
between Do and Dt is Dt ¼ 4=9 Do.
As Figure 18 shows the splitting of d-orbitals, it is evident that for a d10
system in an octahedral or a tetrahedral field, the net energy change due to
splitting is zero.
Consider a d10 system in an octahedral field where the configuration
becomes t2g 6 eg 4 . Now the decrease in energy due to six electrons occupying
t2g is given by 6 ð2=5ÞDo ¼ ð12=5ÞDo, whereas the increase in energy due
to four electrons occupying eg orbitals is 4 ð3=5ÞDo ¼ ð12=5ÞDo. Thus for
a spherically symmetrical system, the algebraic sum of all the energy shift of
all orbitals is zero. The splitting pattern, in which the algebraic sum of the
entire energy shift is zero, is said to obey the centre of gravity rule. Thus, the
‘centre of gravity’ is preserved in the splitting of d-orbitals.
6.1 Ligand Field Stabilization Energy (LFSE)

The splitting of d-orbitals results into the lowering of energy of some of the
orbitals as compared to their equilibrium positions (t2g orbitals in an
octahedral field). Each of the electrons occupying such orbitals results into
the lowering of energy. When the number of electrons occupying the low
energy orbitals is greater than that of the higher energy orbitals, there is a
net lowering of the energy of the system. This energy is called ligand field
stabilization energy (LFSE).
The expression for LFSE can be obtained as follows:
Let us consider an ion in an octahedral ligand field. Hence, the d-
orbitals will split into t2g with lower energy ð2=5 DoÞ and eg with higher
energy ð3=5 DoÞ. Moreover, the amount of energy required for spin pairing
of the electrons will be ‘P’.
Thus, LFSE in an octahedral ligand field can be given as the following:

2
LFSE ¼ Number of electrons in t2g Do þ P
5

3
þ Number of electrons in eg Do þ P
5
While LFSE in a tetrahedral ligand field can be given as the following:

3
LFSE ¼ Number of electrons in eg Dt þ P
5

2
þ Number of electrons in t2g Dt þ P
5
6.1.1 Tetragonal Distortions in an Octahedral Field

Distortions in geometries can further split the d-orbitals. Consider the two
common distortions in an octahedral field:
1. Slowly removing two trans-ligands lying on the z axis.
2. Compressing two trans-ligands lying on the z axis.
Slowly removing two trans-ligands lying on the z axis:
Upon removal of two trans-ligands lying on the z axis, the repulsion
faced by the dz2 orbital decreases significantly, and also a slight reduction in
repulsion is experienced by t2g orbitals with the z-component (i.e. dxz and
dyz), as shown in Figure 19. Thus as expected, the eg orbitals further split into
dz2 with lower energy and dx2 y2 with correspondingly high energy. The t2g
orbitals also split into dxz and dyz with lower energy but dxy with corre-
spondingly high energy. As shown in the figure, it is possible that the energy
of dz2 orbital drops below the energy of dxy. This phenomenon is particularly
observed in the square planar complexes of Co(II), Ni(II) and Cu(II).
Upon compression of these two trans-ligands, as expected, the exact
opposite type of splitting will take place, which is shown in Figure 20.
6.1.2 The Molecular Orbital Theory

For an octahedral complex ML6, let us consider that the ligands have only
six sigma orbitals, viz, (sx, sx, sy, sy, sz, sz) directed toward the metal
ion. These six orbitals must be combined to obtain six ligand group orbitals
in such a way that each of these orbitals is suitable for overlap with only one
of the s, p or d orbitals of the metal, as shown in Figure 21.
Figure 19 Further splitting of t2g and eg orbitals upon removing trans-ligands lying
along the z axis.
Figure 20 Further splitting of t2g and eg orbitals upon compressing trans-ligands lying
along the z axis.
26
Essentials of Coordination Chemistry
Figure 21 Metal orbitals and corresponding ligand group orbitals suitable for overlap.
Figure 22 Molecular orbital diagram showing s-bonding in an octahedral complex.
According to the MO theory, every overlap between ligand group

orbitals and suitable metal orbitals will result into the formation of one
bonding molecular orbital (BMO) and one antibonding molecular orbital
(ABMO). The t2g orbitals of the metals oriented in the plane cannot overlap
with the ligand orbitals, and hence, they become nonbonding molecular
orbitals. The eg orbitals on linear combinations with ligand group orbitals give
doubly degenerate eg and eg* molecular orbitals. The MO’s derived from the
p-orbitals are named as t1u and t1u* , respectively. These MO’s are threefold
degenerate, while the combination of s-orbital of the metal and ligand orbital
results into the formation of molecular a1g and a1g* , respectively.
Figure 22 shows that the six electron pairs donated by ligands can be
accommodated in the six sigma bonding molecular orbitals of the complex,
resulting into the formation of six sigma bonds. From the MO diagram, it is
clear that the MO theory also supports the splitting of d-orbitals into t2g and
eg, as indicated by the LFT.
7. MAGNETISM
While the coordination chemistry was earlier the chemistry of compounds
with coordinate covalent bonds, eventually it became the chemistry of
transition elements with a wide variety of inorganic and organic ligands.

The transition elements are characterized by incompletely filled d-orbitals.
As a consequence, the transition elements and their compounds exhibit
variable oxidation states, give coloured compounds, find application in
catalysis and also have interesting magnetic properties [6]. An introductory
study on the magnetic properties of transition metal complexes is provided
in the following section.
7.1 Diamagnetism
The substances that, when placed in a magnetic field, decrease the intensity
of the magnetic field than that in a vacuum are called diamagnetic sub-
stances, and this property is diamagnetism. The magnetic field tends to
avoid such substances, and as such, diamagnetic substances are weakly
repelled by the magnetic field. All of the chemical substances containing
paired electrons show diamagnetism.
7.2 Paramagnetism
The substances that, when placed in a magnetic field, allow the magnetic
field to pass through them as compared to a vacuum, are called para-
magnetic substances, and the property of showing this behaviour is called
paramagnetism. A paramagnetic substance tends to set itself with its length
parallel to the magnetic field. Thus a paramagnetic substance is attracted
into a magnetic field. The chemical substances containing unpaired elec-
trons show paramagnetism.
7.3 Ferromagnetism and Antiferromagnetism

Ferromagnetism and antiferromagnetism are special classes of para-
magnetism. A simple paramagnetism is observed in magnetically dilute
systems, where the ions containing unpaired electrons are far apart from
each other so that they can behave independently. Ferromagnetism and
antiferromagnetism are observed in magnetically concentrated systems
where the individual paramagnetic ions are very near, and they are affected
by the magnetic moments of each other. In ferromagnetism, the magnetic
moments point in the same direction. Due to this, the magnetic suscepti-
bility of a substance increases to a great extent. Ferromagnetism is observed
in transition metals and some of their compounds. In antiferromagnetism,
the magnetic moments point in the opposite direction. Due to this, the
magnetic susceptibility of a substance decreases to some extent. Antifer-
romagnetism is observed in the salts of ions like Mnþ2, Feþ3 and Gdþ3.
Magnetic susceptibility and magnetic moments are the important

quantities in quantifying the magnetic properties of materials. The magnetic
susceptibility, which is the response of a substance to induced magnetiza-
tion, is represented in various forms like volume magnetic susceptibility
(cv), gram magnetic susceptibility (cg) and molar magnetic susceptibility
(cM). While the parent term, volume magnetic susceptibility is equated as
cv ¼ I/H, which is the ratio of intensity of magnetization to the strength of
the field. The other terms are derived from cv as cg ¼ cv/r (r represents
the density) and cM ¼ cg M (M is the molecular weight of the
substance).
The molar magnetic susceptibility cM is inversely proportional to T i.e.
cM a 1/T hence, cM ¼ C/T.
Where C is a Curie’s constant and the equation is called Curie’s
equation. Ferromagnetism and antiferromagnetism are deviations from the
Curie law. From Figure 23, it is seen that in both cases, the magnetic
susceptibility changes suddenly at a temperature Tc – this temperature is
called Curie temperature. For antiferromagnetism, the Curie temperature is
also called Neel temperature.
The effective magnetic moment for a transition metal complex con-
!
taining unpaired electrons has contributions from both orbital ½ L as well as
!
spin angular momentum ½ S , which can be represented as
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
!! !!
meff ¼ L ð L þ 1Þ þ 4 S ð S þ 1Þ B:M: The spin-only magnetic
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
moment ms can be calculated by the following formulae: ms ¼ 4SðS þ 1Þ
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
or nðn þ 2Þ, which is illustrated below. The formula ms ¼ 4SðS þ 1Þ
can be used to calculate the spin only magnetic moment for a term symbol
for a d2 ion: 3F using a general formula of a term symbol as 2Sþ1L.
Figure 23 A plot of cM / T showing different types of magnetic behaviour.

Thus, for 3F, 2S þ 1 ¼ 3 and hence S ¼ 1.

pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffi pffiffiffi
Now; ms ¼ 4SðS þ 1Þ ¼ 4 1ð1 þ 1Þ ¼ 4ð2Þ ¼ 8
¼ 2:83 B:M:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Similarly, the formula nðn þ 2Þ, where ‘n’ represents the number of
unpaired electrons, can be used for a d2 ion in an octahedral field as
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffi pffiffiffi
ms ¼ nðn þ 2Þ ¼ 2 ð2 þ 2Þ ¼ 2ð4Þ ¼ 8 ¼ 2:83 B:M:
7.4 The Spectrochemical Series

The magnitude of splitting of d-orbitals; Do or Dt is affected by the nature
of the ligand. The electrons occupy the degenerate orbitals according to
aufbau principle, Pauli’s exclusion principle and Hund’s rule of maximum
spin multiplicity. But while filling the last electron in a set of degenerate
orbitals, an option for putting the electron in the next higher orbital instead
of pairing it in the same orbital comes into the picture. The actual action is
decided by comparing the value of Do or Dt, whichever is applicable with
the pairing energy (P). While the pairing energy almost remains constant,
the nature of the ligand affects the magnitude of splitting. Thus, the
complexes of the same metal ion with different ligands sometimes have a
different number of unpaired electrons. Experimental study of the spectra
of a large number of complexes has made it possible to arrange the ligands
in a series based on their capacity to cause the splitting of d-orbitals. This
series is known as spectrochemical series.
I > Br > Cl > F > OH > C2 O4 2 > H2 O > NCS > py
> NH3 > en > bpy > o-phen > NO2 > CN
The initial members of the series cause lower values of the Do and are
known as weak field ligands, while the members toward the late end of
the series cause greater splitting of the d-orbitals and are known as strong
field ligands. The strong field ligands thus cause the electrons to pair in the
degenerate orbitals at the cost of pairing energy. Hence, the resultant
complexes will have low value of the total spin. Such complexes are
known as low spin complexes. A counter-argument explains the defini-
tion of the high spin complexes are formed by weak field ligands like I,
Br, Cl, F and OH. The spectrochemical series has limitations, as only
the most common oxidation states of the metals are considered in making
Figure 24 Only one possible arrangement of electrons in octahedral complexes

containing 1, 2, 3, 8, 9 or 10 d-electrons.
Figure 25 High-spin and low-spin arrangement of electrons in octahedral complexes

containing 4, 5, 6 or 7 d-electrons.
the spectrochemical series, and even with the common oxidation states
of some metals, a small variation in the sequence of members is found
sometimes.
Since the number of unpaired electrons in high-spin and low-spin states
are different, the magnetic moments in the corresponding complexes are
also expected to be different.
As shown in Figure 24, the number of unpaired electrons in the pres-
ence of a strong field and weak ligands remain the same when we have 1, 2,
3, 8, 9 or 10 d-electrons in octahedral complexes.
As shown in Figure 25, the number of unpaired electrons in high-spin
and low-spin states are different for 4, 5, 6 or 7 d-electrons in octahedral
complexes.
8. CATALYTIC PROPERTIES
The transition metals and their compounds are well-known for their catalytic
properties. The works related to catalytic applications involving metallic
compounds have been awarded about 15 Nobel prizes between 1901 and
2014. While the idea of catalysis was originally conceived by Berzelius, it was
Wilhelm Ostwald who was first recognized for a Nobel prize on catalysis in
the field of chemistry. Sabatier, a Nobel laureate (1912), found that the
introduction of a trace amount of nickel to the reaction mixture catalyzes the
hydrogenation of many organic compounds. The Sabatier principle [7] for
catalysis emphasizes on the strength of the interaction between substrate and
catalyst. He mentioned that in order to have a fruitful catalysis of a reaction,
this interaction should neither be too strong or too weak; it should be just
right. Other Nobel-winning achievements in the field of catalysis include the
Haber-Bosch process (1918) for the catalytic manufacture of ammonia and
catalytic cracking using metal oxides. Metallocenes, a class of organometallic
compounds, found application in catalyzing the polymerization of alkenes
containing terminal double bond. These compounds are very popular in the
polymer industry as Ziegler–Natta catalysts [8]. Wilkinson’s catalyst, chlor-
otris(triphenylphosphine)rhodium(I), is a prominent transition metal complex
employed as a catalyst in the hydrogenation of alkenes [9].
The twenty-first century transition metal complex catalysts include
Grubb’s catalysts for metathesis reactions in olefins and Palladium com-
plexes used for coupling reactions in organic chemistry.
A series of transition metal carbene complexes, known as Grubb’s [10,11]
first generation and second generation catalysts and Hoveyda–Grubb’s first
and second generation catalysts, afford metathesis between two olefins. The
metathesis reactions refer to the exchange of the cationic and anionic partners
and may be represented by the following general equations, as in Figure 26.
The mechanisms of these reactions involve a replacement of phosphine
ligand by an olefin and a subsequent metathesis reaction on the metal
complex itself. A variety of Ruthenium carbene complexes used as catalysts
are shown in Figures 27 and 28.
A very important reaction, known as a Suzuki coupling reaction, which
involves the coupling of organic groups by boronic acid and a halide, is
known to be catalyzed by Pd(0) complex [12–14]. The reaction may be
represented as shown in Figure 29.
The mechanism of this reaction involves a shuttle between 0 and þ2
oxidation states of Palladium. The mechanism of this reaction can be
explained by focussing on the reactions occurring on the palladium catalyst.
Figure 26 Simplified representations for metathesis reactions.

Figure 27 Grubb’s first and second generation catalysts.
Figure 28 Hoveyda–Grubb’s first and second generation catalysts.
Figure 29 Suzuki coupling reaction.
In the first step, an oxidative addition of palladium to the halide gives an

organopalladium species. A subsequent reaction with a base and trans-
metallation followed by reductive elimination of the product gives back the
palladium catalyst, completing the catalytic cycle. The complex involved in
the catalytic cycle bears the general formula: [ArPd(OR)L2].
9. EXERCISES
9.1 Multiple Choice Questions
1. What is the spin multiplicity of the electronic state ‘3P’
(a) 1 (b) 1=2
(c) 3 (d) 2
2. Antiferromagnetism is a type of —————
(a) Magnet (b) Diamagnetism
(c) Paramagnetismt (d) Ferromagnetism
3. CN is a ——————————— field ligand.
(a) Bidentate (b) Octahedral
(c) Strong (d) Weak
4. What is the value of ‘L’ for 1D?
(a) 4 (b) 1
(c) 2 (d) None
9.2 Short/Long Answer Questions

1. Giving suitable diagrams, describe the splitting of d-orbitals upon the
introduction of an octahedral and tetrahedral ligand field.
2. What is centre of gravity rule? How does it apply to the splitting of the
d-orbitals in the octahedral and tetrahedral ligand fields?
3. Prepare a diagram that traces how the d-orbital splitting pattern
changes as an octahedral complex is altered via tetragonal distortions.
4. Explain how the MO theory supports the splitting of d-orbitals as indi-
cated by the crystal field theory.
5. By using orbital splitting diagrams, show which dn electron configura-
tions are capable of giving both low-spin and high-spin configurations
in an octahedral ligand field.
6. Give an account of the magnetic properties of transition metal complexes.
7. Calculate the spin-only magnetic moments in d4, d5, d6 and d7 com-
plexes in both low-spin and high-spin configurations in an octahedral
ligand field.
8. What is a spectrochemical series? What are its limitations?
9. Calculate the LFSE in the units of Do for the following high-spin ions
in octahedral fields Feþ2, Mnþ2 and Coþ2.
10. Predict the magnetic properties and LFSE for each of the following
[Fe(CN)6]3, [Co(NH3)6]þ3, [Co(Cl)4]2 and [Fe(H2O)6]3.
SUGGESTED FURTHER READINGS

The topics discussed in this chapter are a part of standard graduate curriculum. A majority of
the textbooks with titles related to basic coordination chemistry can act as a source of further
reading. Moreover, there are several web resources useful for further learning. Some of them
are listed below.
http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch12/complex.
php#werner
http://www.britannica.com/science/coordination-compound
http://nptel.ac.in/courses/104103069/20
http://www.chem.iitb.ac.in/people/Faculty/prof/pdfs/L5.pdf
REFERENCES
Attempts have been made to include some illustrations from the books and research articles
listed below.
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chemistry. Academic Press; 1949. p. 253.
[2] Connelly NG, Royal Society of Chemistry (Great Britain), International Union of
Pure and Applied Chemistry. Nomenclature of inorganic chemistry. IUPAC recom-
mendations 2005, vol. xii. Cambridge, UK: Royal Society of Chemistry Publishing/
IUPAC; 2005. 366 p.
[3] House JE, House KA. Chapter 19–Structure and bonding in coordination compounds.
In: House JE, House KA, editors. Descriptive inorganic chemistry. 2nd ed. Amsterdam:
Academic Press; 2010. p. 441–78.
[4] Burns G. Chapter 8–Crystal field theory (and atomic physics). In: Burns G, editor.
Introduction to group theory with applications. Academic Press; 1977. p. 156–98.
[5] Graddon DP. Chapter II–Modern theories of co-ordination chemistry. In: Graddon DP,
editor. An introduction to co-ordination chemistry. 2nd ed. Pergamon; 1968. p. 24–54.
[6] Earnshaw A. V–further topics. In: Earnshaw A, editor. Introduction to magneto-
chemistry. Academic Press; 1968. p. 70–83.
[7] Medford AJ, et al. From the Sabatier principle to a predictive theory of transition-metal
heterogeneous catalysis. J Catal 2015;328:36–42.
[8] Coates GW, Waymouth RM. 12.1–Transition metals in polymer synthesis: Ziegler–
Natta reaction. In: Wilkinson EWAGAS, editor. Comprehensive organometallic
chemistry II. Oxford: Elsevier; 1995. p. 1193–208.
[9] Pettinari C, Marchetti F, Martini D. Metal complexes as hydrogenation catalysts. In:
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2003. p. 75–139.
[10] Penczek S, Grubbs RH. 4.01–Introduction. In: Möller KM, editor. Polymer science: a
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[11] Grubbs RH, Pine SH. 9.3–Alkene metathesis and related reactions. In: Fleming BMT,
editor. Comprehensive organic synthesis. Oxford: Pergamon; 1991. p. 1115–27.
[12] Moriya T, et al. A new facile synthesis of 2-substituted 1,3-butadiene derivatives via
palladium-catalyzed cross-coupling reaction of 2,3-alkadienyl carbonates with orga-
noboron compounds. Tetrahedron 1994;50(27):7961–8.
[13] Miyaura N, et al. Palladium-catalyzed cross-coupling reactions of B-alkyl-9-BBN or
trialkylboranes with aryl and 1-alkenyl halides. Tetrahedron Lett 1986;27(52):6369–72.
[14] Miyaura N, Yano T, Suzuki A. The palladium-catalyzed cross-coupling reaction of
1-alkenylboranes with allylic or benzylic bromides. Convenient syntheses of 1,4-alkadienes
and allybenzenes from alkynes via hydroboration. Tetrahedron Lett 1980;21(30):2865–8.
CHAPTER 2
Basic Concepts of Symmetry

and Group Theory
Contents
1. Introduction 38
2. Symmetry Operations and Elements of Symmetry 38
2.1 Rotation 38
2.1.1 Linear Molecules 39
2.1.2 Angular Molecules 39
2.1.3 Triangular Molecules 39
2.1.4 Square Planar Molecules 40
2.1.5 Tetrahedral Molecules 41
2.1.6 Trigonal Bipyramidal Molecules 41
2.1.7 Octahedral Molecules 42
2.2 Reflection 44
2.3 Improper Rotation (Rotation–Reflection) 45
2.4 Inversion 47
3. Point Groups 49
3.1 Symmetry Group 49
3.2 Point Group 49
3.3 Some Point Groups 49
3.3.1 Cn, Cs and Ci Groups 49
3.3.2 Cnv Groups 52
3.3.3 Cnh Groups 54
3.3.4 Sn Groups 54
3.3.5 Dn Groups 54
3.3.6 Dnd Groups 55
3.3.7 Dnh Groups 55
3.3.8 Cubic Point Groups 57
3.4 Properties of Point Groups 58
3.5 Conjugate Elements 59
3.6 Class 59
4. Flow Chart for Determination of Molecular Point Groups 59
5. Exercises 60
5.1 Multiple Choice Questions 60
5.2 Short/Long Answer Questions 61
Suggested Further Readings 62
Essentials of Coordination Chemistry © 2016 Elsevier Inc.

http://dx.doi.org/10.1016/B978-0-12-803895-6.00002-1 All rights reserved. 37
1. INTRODUCTION
The symmetry of molecules and solids is a very powerful tool for devel-
oping an understanding of bonding and physical properties of various
chemical entities. At the same time, it allows a learner to quantify the
beauty of molecules with different shapes. The knowledge of symmetry is
useful in predicting the nature of molecular orbitals. It also helps in pre-
dicting whether electronic and vibration spectroscopic transitions can be
observed. The presence and absence of elements of symmetry in molecules
leads a chemist to predict the possible optical isomerism in molecules. Thus,
symmetry becomes an important tool in the hand of a theoretical and
inorganic, as well as an organic, chemist.
2. SYMMETRY OPERATIONS AND ELEMENTS

OF SYMMETRY
2.1 Rotation
Rotation is an operation referring to a circular movement of an object
about an axis passing through the centre of an object.
One full rotation corresponds to a movement of 360 about an axis, and
it is the same as a rotation of 0 (practically no rotation). Thus, after a
rotation of 360 , the appearance of the original object and the resultant
object always remain indistinguishable.
The axis of rotation is named as Cn, where n represents the number of
times indistinguishable appearance was obtained upon rotation of 360 . If
n ¼ 1, the rotation is through an angle of 360 , which means no change to
the molecule. Thus C1 means identity operation (E), which leaves the
molecule unmoved. Doing no change to the object is called identity
operation. This operation is needed for mathematical completeness. Every
molecule has at least this symmetry element.
An object can have more than one axis of rotation about which an
indistinguishable appearance of the object is obtained more than once upon
rotation of 360 .
The axis with highest value of n is called the principal axis.
Axes of rotation in a few hypothetical molecules with one- and two-
dimensional geometries are discussed in the following section.
Basic Concepts of Symmetry and Group Theory 39
Figure 1 Infinite fold rotational axis (CN) and infinite number of C2 axes in a linear
molecule.
2.1.1 Linear Molecules

A diatomic molecule rotated along the axis, as shown in Figure 1, becomes
indistinguishable infinite times (remains indistinguishable) during the
rotation of 360 , hence the axis is named as CN, which is the principal axis.
There are infinite numbers of axes perpendicular to CN and passing
through the centre of the molecule, which yields the original appearance
twice during a rotation of 360 . All these axes are named as C2 ; C20 ; C200 and
so on.
2.1.2 Angular Molecules

A triatomic angular molecule of the type A3 or AB2 becomes indistin-
guishable twice during the rotation of 360 , hence the axis is named as C2,
as shown in Figure 2.
2.1.3 Triangular Molecules

A triatomic triangular molecule of the type AB2 becomes indistinguishable
twice during the rotation of 360 , hence the axis is named C2. It has three
such axes passing through each of the atoms and coincides with the centre
of the molecule. Such molecules have a C3 axis (principal axis)
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green turf the school buildings peered back at them from behind
nearly leafless trees. It was twenty minutes past one then, and the
game was to start at two-fifteen, but already there was a trickling
stream of folks crossing the far side of the field in the direction of the
iron stands. Many automobiles, too, were in place beyond the ropes,
and the occupants were having picnic lunches there. Above the
grandstand a big brown flag bearing a white W waved and whipped
in the wind. The sun was doing its best for the occasion. It made the
freshly drawn lines of the gridiron gleam, gave the dying grass a real
semblance of summer verdancy, found a clump of birches on the
nearby hillside that still held their leaves and made a golden
splendor of them and, flashing against the varnished surfaces of the
parked cars, created blobs of light that dazzled the eyes. And over
there, too, it discovered a fluttering blue pennant bearing a white W
and illumined it gloriously.
In the field house Dan Farrell, the trainer, laid out the contents of
his bags and the haunting odor of his own special liniment
permeated the quarters. The call to change into togs came at half-
past one and at a quarter to two they were all ready. Mr. Babcock
and Mr. Hilliard and Mr. Connover ended their low-voiced conference
in a corner and herded the players outside to the sunlit porch. It
wasn’t one of the coaches, though, who spoke to them then. It was
Captain Dave Lothrop, and partly because Dave never did say much
and even now couldn’t find the right words, although he tried hard
enough, his little speech got under their skins. He didn’t say anything
new. Indeed, what is there new that may be said at such times? It
has all been said over and over again, hundreds, thousands of
times, since the first football team was formed. But Dave,
floundering, seeking desperately for words, his eyes fixed on the
barred field over yonder, managed to endow old sounds with a fresh
meaning.
“Coach says we can do it, fellows,” said Dave. “He’s not lying to
us. Besides, I know, too. I know that if we think—if we just say we
can lick ’em—go out there and fight every minute, every second, just
forgetting everything but beating Wolcott—why, I know we can,
fellows! We’ve got to fight, fight hard. Well, we can do it. We’ve got to
fight harder than they fight. We can do that, too. I—I wouldn’t want to
lead you fellows out there if I wasn’t certain right down to my boots
that you meant to lick those guys. Think what it would be like to go
back to Wyndham to-night beaten. We couldn’t face the School!
Why, hang it, we’ve got to win! That’s all there is to it. We’ve got to
win! And when you’ve got to do a thing, you—you”—Dave’s gaze
came back from the gridiron and challenged them—“you do it, if
you’re not yellow! Well, that’s all. Only”—Dave shot out a big fist
—“tell me this. Are you going to fight? Are you going to win?”
“Yes!” The reply was an explosion of pent-up emotions, a
determined, defiant, exalted burst of sound that carried far across
the sunlit field.
“Come on, then!” said Dave.
Twenty minutes later the gridiron was empty again. A silver half-
dollar had spun into the sunlight and dropped to the turf. Captains
and officials were back on the side-lines. The raucous blaring of the
Wolcott Student Band was stilled, the cheering had momentarily
hushed and the throng that filled every seat in the stand and
overflowed along the ropes drew coats and wraps higher, resettled in
their places and braced themselves for the fray. Then eleven brown-
stockinged youths ran out from one side of the barred battlefield and
eleven blue-stockinged youths from the other, and the cheers began
again and the Wolcott bass-drummer thumped mightily and several
thousand persons, many of them normally unemotional, experienced
a sudden shortness of breath accompanied by a fluttery sensation of
the heart. And at about that moment, on the east side of the field, a
man in a black derby confided to a man in a chauffeur’s livery that,
“That’s the captain of our side, Henry. Lothrop his name is. He’s to
kick the ball away.”
“With them long legs, and the powerful looks of him,” responded
his companion with relish, “I’m thinkin’ them other laddies’ll be
chasin’ it back to the hills yonder!”
That no such performance as that was contemplated or desirable
was being explained when the ball sailed up and away and the
informant relapsed into silence. Somewhere at the north end of the
field a player caught the pigskin, tucked it against him and went
down before he had taken two strides. The Wyndham cheers burst
forth, high and sharp. Wolcott tried the Wyndham left and was
repulsed, shot her fullback at Desmond and got three yards and then
punted far, the wind that quartered the gridiron adding a good ten
yards to the kick. Wyndham ran the ball back six yards or so, tried
two slams at the brown line and punted back to Wolcott’s forty. The
ancient enemies were trying each other out.
Wolcott got three yards outside Cotter and two more through
Captain Dave, but a five-yard penalty set her back and again she
punted on third down. This time the ball rolled over the line. Jensen
got free around Wolcott’s left end and carried the pigskin on the first
down to the twenty-eight yards. Ogden, from kicking position, tried a
straight buck on right tackle and was thrown for a yard loss. Jensen
made two outside left tackle and Ogden punted short to midfield,
where the ball went out. Not until the quarter was almost over did
either team bid for a score. Then Wolcott tried a short forward-pass
over the center that grounded and followed it from the same
formation with a fake that sent left half around the right for fourteen
yards and placed the ball on Wyndham’s twenty-eight. A cross-buck
on Cotter failed of an inch and Wolcott again threw forward. This
time the throw was long, fast and low and aimed at the corner of the
field. Over there, close to the goal-line, the Brown’s left halfback
turned as the pigskin sped forward. Four strides would have taken
him across, but, although he had skillfully eluded the Wyndham
defense until now, Nemesis, in the form of Pete Jensen, was at
hand, and while Pete couldn’t get in position to steal the catch he
could and did bat the ball aside.
With two downs left, Wolcott sent her fullback outside right tackle
from kicking position and gained four yards, placing the ball on the
twenty-four. From the thirty-three, with quarterback holding the ball,
Johnson, Wolcott’s rangy left tackle, tried a goal from placement
while the Wyndham cohorts held their breaths. Johnson had the
quartering gale to figure with, and it seemed that he underestimated
the force of it, for the pigskin, while it started true enough, met the
full strength of the wind before it had covered half the distance and
swerved widely to the left. Not until an official waved his arms
negatively, though, was Wyndham certain that the effort had failed.
A minute later, after Wyndham had punted, the whistle blew and
the teams made for the water pails. The Wolcott band came to life
again, and the cheer leaders swung their megaphones. Then
Wyndham took the north goal and faced the enemy on the thirty-nine
yards. There were no changes in the Wyndham line-up. Archer and
Drayton were still the ends, Cotter and Weldon the tackles, Lothrop
and Desmond the guards, Carlson the center, Stoddard the quarter,
Whitemill and Jensen the halfs and Ogden the fullback. Nor had
Wolcott yet altered her team. The opposing elevens were strikingly
alike in appearance. Each presented a center trio of big, fairly heavy
men closely matched for height and weight. Each featured fast,
rangy tackles and rather light ends. In the backfield Wolcott had a
slight advantage in weight, for James, her fullback, was a fellow after
“Big Bill” Fargo’s style, although he lacked Fargo’s ability to start
quickly and was far less dangerous on end runs. Wolcott’s quarter
had weight and carried the ball frequently. Her halfbacks were fairly
light and showed speed. One, Hoskins, had already proved himself a
very shifty player.
The second period saw a good deal of old-fashioned football on
the part of Wolcott and a punting game on the part of the opponent.
Wolcott used straight plunges and slants with sufficient success to
take her to the Blue’s thirty-six yards. There her gains lessened and
two sweeping plays and two forward-passes took her no further than
the twenty-seven, where she yielded the ball. Hoskins was the
Brown’s forward-pass ace, but Hoskins was so closely watched that
he was unable to show anything. Wyndham punted on second down
and watched for a break. With that wind quartering the field a fumble
by a Wolcott back would have surprised no one. But the break didn’t
come. Wolcott declined to catch the punts after two narrow escapes
and the ball was allowed to roll, twice going over the goal line for
touchbacks. Four penalties were handed out by the referee, two to
each team, but none affected the fortunes of the game appreciably.
The whistle ended the half fifty-two minutes after the kick-off.
CHAPTER XXIV
WATTLES AGREES
T he teams trailed off and the rival cheering sections became

concertedly vocal once more. One had to either cheer or sing if
only to keep warm! The Wolcott songsters followed the band through
a martial effort that wasn’t a great success because most of the
fellows had forgotten the words and sang “dum-ti-dum-dum” instead.
Then Dodson, Wyndham cheer captain, tossed aside his big blue
megaphone and threw his arms aloft.
“Let’s have ‘We Beat Her,’ fellows! Everybody into it and make it
snappy. All right! ‘We-e-e—’!”
Whereupon the visiting contingent answered with their latest
effusion, sung to the tune of a popular ballad of the year:
“We beat her back in ’16, in ’17 once more;

We swamped her in ’20 with a sixteen-nothing score!
We beat her in ’21 when she couldn’t hold the ball,
But this year, on her own field, we’ll beat her worst of
all!”
Wyndham had no band to aid—or hinder—but she made the

welkin ring. Dodson, white-sweatered, leaped and danced and kept
time with waving arms and swaying body. “Great! Once more now!
All sing!” They responded valiantly, louder than before since many,
previously silent, found courage and lifted their voices. Wolcott
applauded and laughed and came back with a derisive composition
in which “Wyndham” was insultingly punned with “wind ’em.”
Across the field, Mr. Deane lighted a fresh cigar and said: “Well, it
looks as if they’d pulled that fellow’s teeth, eh? What’shisname, I
mean.”
“Hoskins?” asked Loring. “Yes, I don’t believe he will trouble us
much, father. Mr. Babcock set two men to covering him and he
hasn’t got away with anything yet. What Wolcott may do, though, is
fake a throw to Hoskins and send the ball the other way. That might
catch us napping.”
“How did you spy that fellow, Lory?”
“They ran him on near the end of last week’s game. Wolcott had
scored a touchdown and a field-goal in the first half and sent her
first-string men off to the showers. After that she couldn’t do much.
The other team got scrappy and held Wolcott twice inside its twenty
yards. I think Wolcott thought she ought to have one score at least to
show for the last half and took a chance. Anyway, after she’d used
up two downs over there near the twenty-five-yard line she called
Hoskins in, and he sifted through on the first play and trotted down to
the corner of the field, just as he did a few minutes ago. The ball
went right into his hands and he stepped over the line for a
touchdown. Then he was taken right out again. I saw the trainer
hand him his sweater and send him back to the gym. That was all I
needed to see, sir.”
Mr. Deane chuckled, and Mrs. Deane said admiringly: “I think that
was very, very clever, dear.”
“Thanks, moms, but it really wasn’t. Any one could have called the
turn. I suppose they thought we didn’t know that they’d been working
up that forward-passing stuff under cover. They’d kept it pretty well
hidden. If they had thought twice, though, they wouldn’t have shown
their hand like that.”
“It’s safe to say they wish they hadn’t,” chuckled Mr. Deane. “I
suppose they’re wondering now what happened, eh?”
“They know what happened,” laughed Loring, “but it’s a bit late! I
wish we had managed to get one score in that half, though. Wolcott
will come back pretty hard, I guess.”
Both teams had made changes when they faced each other once
more. For Wyndham, Williams was at left end, Couch at right end,
Higgs at center, Breeze at right guard and Houston at quarter. The
Blue chose the north goal and kicked off to Wolcott. The wind had
decreased perceptibly and grown flukey, and Ogden’s kick-off went
out of bounds on Wolcott’s twenty-seven yards. Three minutes later
the Brown had crossed the middle of the field and taken the pigskin
into Wyndham territory. Faking a forward-pass, she sent her left half,
a fresh player who had relieved Hoskins, on a wide run around the
right end. Couch was neatly boxed and the ball went to the thirty-four
yards. Wolcott was going now. Concentrating on the Wyndham left,
she made first down on the twenty-two, sending Cotter out of the
game. Longwell took his place. Wolcott tried Longwell and made a
scant two. A short heave over tackle on the right bounded out of the
catcher’s hands, was fumbled by Ogden and grounded. With eight to
go on third down, Wolcott elected to try a field goal. She attempted
one more smash first, though, and pulled in another two yards
through Captain Lothrop. Then the ball shot back to her right tackle,
who had retreated to the twenty-nine yards, and, although the
Wyndham forwards tore through desperately, arose again safely and
sailed squarely across the bar for the first score.
The Brown’s adherents went wild with joy, the big drum boomed,
and automobile horns blared stridently. Wyndham’s cheer, though,
was loud and undismayed as the teams went back to midfield.
Wolcott kicked off. Houston caught, juggled for a heart-breaking
instant, dodged the first Wolcott end and then plunged straight
ahead. A second tackler tried, missed and went down. A hasty
interference formed about the runner, Weldon in the lead, mowing
down the enemy. At the thirty-six yards, forced away from his
interference, Houston was pulled to earth after a stirring run of thirty
yards.
Wyndham kept the ball to Wolcott’s thirty-nine, Ogden and Jensen
alternating at slants that tore off four, five, once eight yards. On the
enemy’s thirty-nine an off-side penalty set the Blue back and, after
two plunges that netted little, Ogden punted to the Brown’s five. The
Wolcott quarter refused the catch and the ball bounced erratically
back in the direction it had traveled. Weldon put it down on the
fourteen yards. Wolcott tried one off-tackle play from kick formation
and gained three. Then she punted, James, her fullback, standing
close to the five yards. Lothrop broke through and hurried the kick
and the pigskin went high and was shortened by the wind. Jensen
caught close to the side-line on Wolcott’s thirty-two, made three and
was thrown out.
The Blue took up her journey again, a short pass, Ogden to
Houston, yielding seven yards and Ogden carrying the ball through
the right side for a first down. Wyndham cheerers were chanting
“Touchdown, Wyndham! Touchdown, Wyndham! Touchdown,
Wyndham!” Wolcott asked for time and put in a fresh left guard.
Ogden ran up against a stone wall on the next play and Jensen was
nabbed trying to slide off left tackle, and Captain Lothrop stepped
back to the thirty and held out his hands. When the ball came he
plunged straight ahead and got four through the center. Tom Kemble
reported and Whitemill went off. Tom went back to kick. Higgs
passed badly and the ball reached him on the ground. There was no
time to straighten up and get the kick off, for Wolcott was piling
through on him. So Tom thumped the ball to his stomach and started
off to the right. He dodged one enemy, squirmed free of another,
turned sharply in, twisted and turned and finally went down. He had
added three yards, but three was not enough.
Wolcott decided to punt out of danger on first down and James
went back to the four yards. This time it was the Wolcott center who
offended, and the ball reached the fullback above his head. He
caught it, but both Lothrop and Weldon had broken through and
were bearing down on him on each side. The ball went no farther
than Weldon’s upflung arm and then bounded back. James was
down, but a Wolcott halfback won the race to the ball, picked it up on
the bound and sought to circle the goal. Dave Lothrop brought him
down just short of the line and Wyndham had a safety, two points to
flaunt against Wolcott’s three!
Wolcott kicked from the thirty-yard line, and the quarter ended
after Kemble had caught on his own thirty-two and carried the ball to
the thirty-seven.
For the last period Wyndham had the wind against her, but it was
now little more than a strong breeze, and occasionally the big brown
flag above the grandstand fell limply about the staff. More changes
were made by Mr. Babcock. Archer went back at left and Carlson at
center. Raiford took Weldon’s place, Sproule went in at right half and
“Swede” Hanbury relieved Ogden. Wyndham made four changes in
her line, sending back three veterans of the first half, and introduced
a fresh quarter.
Wyndham reached midfield on six plays, only to lose the ball when
Sproule fumbled. Wolcott was then first down on her own forty-eight
yards. On the first play a penalty for holding set her back to her
thirty-three. A long pass over the right end went astray and a second
attempt on the other side was no more successful. James punted
short and the ball went out at Wyndham’s forty-seven. Breeze was
taken off and Clem Henning succeeded him at right guard. Sproule
got free outside tackle and took the ball to the opponent’s forty-one.
Hanbury made three and then four over right tackle. Kemble was
thrown for a loss on an attempt at the Wolcott left end and Hanbury
punted. The ball went over and was brought back to the twenty.
Wolcott was playing for time now, satisfied, it seemed, with her
one-point lead. She made it first down on her thirty-two with a short
and unexpected forward toss and then, faking a second throw, tore
through Henning for six. Hanbury, who made the tackle, was hurt
and time was called. Presently he went off, assisted, and Johnny
Thayer raced on. Wolcott struck a snag on the next play and lost two
yards. A forward-pass over left guard grounded, after being juggled
by half the players, and James kicked. Again the punt fell short and
the ball was Wyndham’s on her forty-four yards. Raiford gave way to
“Wink” Coles and Couch to Clif Bingham.
The Blue crossed the half-way mark on two plays with Johnny
Thayer carrying, each play a fake cross-buck in which the halfbacks
went outside tackle and the fullback drove straight through guard.
Wyndham had used few split interference plays so far and Wolcott
was easy prey; Johnny got four yards through right guard and seven
through left. Kemble crashed at left tackle for three more and then
went outside the same player for four. Thayer added two through
center, and, with less than one to go on fourth down, Houston cut
through left guard for the distance. Sproule again got loose around
his left and reached the enemy’s twenty-six before he was forced
over the line. Thayer made two and Kemble two and Houston went
back to kicking position. The play was a short pass, however, and
Clif, on the catching end, failed to get his fingers on it. Time was
called for Captain Dave and, after Dan Farrell had worked over him,
Wyndham took a two-yard penalty, Captain Dave staying in. Houston
took a good pass from Carlson and got the ball away cleanly, but it
fell short of the bar.
Time was growing short and the figures on the scoreboard looked
to be final. James punted on first down and put the oval down near
the opponent’s forty-five, his longest punt of the day. Tom Kemble
misjudged and Houston got the ball on the bound and was thrown
savagely on his thirty-six. Time was again called, and when play was
resumed, Stoddard was back at quarter. Wolcott had seized the
opportunity to bolster up her line with a new tackle and end on the
left. Stoddard used a fake cross-buck again and Thayer found a wide
hole at the left of center and romped through for twelve yards. On a
similar play he was downed on the line. There were two minutes left.
Kemble tried the end and made a yard and Sproule had no better
luck off tackle. Kemble went back and hurled across the center to
Stoddard for eight yards and a first down. With Kemble back again,
the ball went to Thayer, and Johnny got six on a sweep around right
end before he was smothered. Sproule and then Kemble hit right
guard and made it first down again. The ball was on Wolcott’s thirty-
one yards and there was just under a minute of playing time left.
Captain Lothrop went out, cheered to the echo, and Smythe took
his place. Ellison went in for Carlson and Treader for Sproule.
Wyndham was still cheering valiantly, hopefully. Treader,
squandering all the pent-up energy and longing of the afternoon in
one brief instant, dashed himself fiercely at the enemy’s right and
squirmed and fought through to the twenty-six. Wyndham roared in
triumph and automobile horns sounded raucously.
“Touchdown! Touchdown!” chanted Wyndham, while Wolcott
implored her warriors to “Hold ’em! Hold ’em! Hold ’em!” Then Tom
again went back and the visiting cheerers changed their slogan.
“Kick that goal! Kick that goal!” was the cry now. Out on the field the
effect was only of so much sound, confused, meaningless, and
Houston had to shout high to be heard.
“30, 87, 27!”
Archer swung away from the line and ran back toward his own
goal. Tom held his long arms out. The timer’s watch told twenty
seconds left. The signal came again:
“30, 87—”
The ball left Ellison and sped back to Tom. Archer swung to the left
and crossed behind. Tom, too, was running that way now, the ball
before him, and so were Treader and Houston, and so carefully were
they spaced that not one of the enemy save the left end saw the ball
pass from Tom to Archer behind that moving screen. But that left
end, coming through inside Clif Bingham, was not able to use his
knowledge to advantage, for Treader crashed into him and he went
down, sprawling in the path of the runners. The Wolcott right end,
speeding around, met Thayer, and that fact kept him, too, forever out
of the play. Treader and Houston swept on around the right, but Tom,
slackening speed, tarried while Archer, still running toward the side-
line, found his position for the throw. Then a Wolcott tackle came
plunging up, and Tom had his work cut out for him. As he and the
brown-stockinged foe met, Archer dropped his right arm behind his
shoulder, swept it forward again and threw, straight and hard, down
the field from the thirty-six yards.
No one had seriously interfered with Clif when the ball had been
snapped. Dodging wide, he had let the Wolcott left end past inside
him. Then, warily, as though only desirous of avoiding the rough
encounters behind, he sped none too hurriedly across three white
marks. The Wolcott left halfback started toward him, but after one
stride changed his course. To him the play was what it seemed, a
fake kick and a wide sweep about the left of his line, and he hurried
up to get into it. Midway between the five-yard-line and the ten Clif
stopped and swung about. If the play had been timed right the ball
should be already on its way. It was. So, too, was the Wolcott
quarterback, and, further away, others. But the ball came faster than
they, and it came true.
Clif set himself, held his hands out for it, felt it thump into them,
tightened his clutch about it, turned and ran. There was but one
white mark to cross before the goal-line, and he had spurned it
before the enemy reached him. Then came the supreme test. The
Wolcott quarterback launched himself forward, but Clif had
anticipated the tackle by the fraction of a second. He twisted to the
right, perilously close to the side-line, spun, saw the enemy go
sprawling past, hands clutching, emptily, leaped the falling body and
was safe. There was the last white streak a stride away and he had
crossed it before the second enemy reached him, crossed it and
dropped to earth, the battered ball held tightly wrapped in his arms!
The Wyndham Team held its banquet on Wednesday night at the

Inn. There were many speeches made and many songs sung, and a
whole batch of congratulatory messages were read by Captain
Dave. There was one from Coach Otis and another from “Big Bill”
Fargo amongst them. Nearly forty persons occupied the three big
tables that had been placed end to end, but all were not team
members. Besides the coaches, and Dan Farrell, the trainer, and Mr.
Frost, representing the Faculty, there was a boy in a wheel chair.
Several speakers of the evening had done their best to embarrass
this guest; notably Mr. Babcock who had gone into sickening details
in his account of how Wyndham had spiked Wolcott’s guns. But
Loring bore up very well, for, after all, he was only human, and he
had done his bit toward that 8 to 3 victory. They sang that charming
ditty “We Beat Her” several times, though now the last line had been
altered to “And what we did last Saturday we’ll do again next fall!”
And finally they sang “Shadowed Walls,” all standing, and cheered
for Wyndham—the long cheer with nine booming “Wyndhams” on
the end—and broke up.
Wattles, waiting outside the door, took charge of Loring, and the
wheel chair trundled along Oak Street with Clif on one side and Tom
on the other. Ahead of them and behind echoes of the evening
sounded. Carlson and Jensen, arms entwined, confided to a star-
sprinkled sky that “We beat her back in ’16.” Farther behind a cheer
arose. Tom, who had emptied the contents of a dish into a pocket
before leaving, shared salted nuts with the others. Wattles’s refusal
to partake availed him nothing. Tom stopped traffic while he filled
Wattles’s mouth, and for some distance Wattles couldn’t have
spoken had he wanted to.
“Wonder who they’ll elect Saturday,” mused Clif a moment later.
“Houston or Ogden,” said Tom. “Say, look here, you fellows! Here’s
something I’ve had on my mind for days. How—”
“Where did you say you’d had it, Tom?” asked Loring. “I’m afraid I
didn’t hear you right.”
“Shut up. Say, how many of the old Scrub fellows do you think
were on the team when we made that touchdown?”
“Four,” said Loring. “You, Clif, Thayer—”
“Wrong, old son! Five! Count ’em! Five! Clem Henning—”
“Oh, well,” objected Clif, “he was off the Scrub long before—”
“Doesn’t matter! And who won their old game, anyway? Why, the
old Scrub won it! Henning was right guard, ‘Wink’ was right tackle,
Johnny took the pass from center, Clif made the touchdown and I—
er—supervised it! Now, then, I ask you, who won the old ball game?”
Three voices answered loudly, proudly and in chorus “The Fighting
Scrub!” And—
“Hooray!” said Wattles, still articulating with difficulty. “Quite so,
sir!”
THE END
BY RALPH HENRY BARBOUR
Yardley Hall Series
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The boy who likes football will find a good technical description of
the game in this book as well as a fine story showing how the newest
tactics work out in practice.
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life of the hero. Baseball has a large place in the story, but other
school events are entertainingly described.
Winning His “Y”

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Pennimore when he arrives at Yardley, due to his father’s millions.
How he lives them both down and wins his “Y” make an exciting
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For Yardley
Another Yardley story with Gerald Pennimore well to the fore
among the characters. Why Gerald was put on probation and how he
bore his punishment are the chief matters of interest.
Change Signals
Kendall Burtis comes from the country and this is the story of how
he develops into a star kicker and the hero of the big game of the
season.
Around the End

Kendall Burtis has developed into a star player, when suddenly it
is discovered that someone has turned traitor and sold the team’s
signals to Broadwood. Kendall is accused, and the outcome is a
surprise to everyone.
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ESTABLISHED FAVORITES FOR BOYS
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By Joseph A. Altsheler
Using the stirring facts of American history and the romance of
real frontier life, Joseph Altsheler writes in the Young Trailers Series
(eight books which may be read independently), tales of thrilling,
daring and actual achievement.
THE HALF BACK
By Ralph Henry Barbour
In this, the most famous of all his famous stories of school and
college life and sport, Barbour combines the sound ideals and the
exciting incidents which have made him a favorite.
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There is always keen interest in an Indian story. Little Smoke gives
a real picture of Indian life, and at a stirring and significant time—that
of the Custer Massacre.
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“School’s too slow, I want to go to work,” said Steve Benton. What
he learned by following that course is told in an unusual and splendid
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By Walter Camp
The great Yale athletic authority puts all his knowledge of football,
of college and the men who go there, and all his magnificent
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A true story of the sea, of warships, of battle, and of glorious
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By GORDON HALL GEROULD $1.75
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Stories by famous writers, all dealing with the things in which
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No part of this publication may be reproduced or transmitted in any form or by any

Library of Congress Cataloging-in-Publication Data

For information on all Academic Press publications

This book is an outcome of my research programmes, coupled with

this is expected to be a camera-ready set of lectures that can be readily

Basic Coordination Chemistry

Essentials of Coordination Chemistry © 2016 Elsevier Inc.

Figure 1 Structure of alizarin dye.

[Cu(NH3)4]þ2, was recorded upon contact between brass alloy and

Figure 2 Bonding in NH3BF3.

Figure 3 First and second coordination spheres in [Co(NH3)6]Cl3.

Figure 4 Secondary valency of Co(III) in [Co(NH3)6]Cl3.

Dentate character is a property of a ligand representing a number of

Ethylenediamine (en), neutral, bidentate

Acetyleacetone (acac), neutral, bidentate

2-hydroxylbenzaldehyde also known as

Dimethylglyoxime(dmg), anionic, bidentate

2,2′-bipyridine, neutral, bidentate

Figure 5 Structures and characteristics of a few important ligands.

Nitrilotriacetic (nta), anionic, quadridentate

2,2ʹ,2ʹʹ-triaminotriethylamine (tren), neutral,

1,2,3-trihydroxypropyl hydrogen carbonate

2-aminosuccinic acid also known as

Figure 6 Structures and characteristics of a few chelates.

Polynuclear complex is a complex with more than one metal atom/

2.1 For Writing the Coordination Formula

2.2 For Writing the Names

2. In a complex (cationic, anionic or neutral), the names of the ligand are

the name of the ligand, as in M-SCN-, it is written as thiocyanato-kS

3. THEORIES OF BONDING IN COORDINATION

Figure 8 Covalent and coordinate covalent bonding in BF3NH3.

valence bond theory (VBT), which is actually an extension of Lewis theory

4. GEOMETRIES OF COMPLEXES WITH DIFFERENT

as it involves minimum ligand–ligand repulsion. These complexes

Figure 9 Hybridization explaining the bonding in [CuCl2].

Figure 11 Tetrahedral Be(acac)2 chelate.

Figure 12 Square planar [Ni(CN)4]2 complex ion.

deformation. However, [CuCl5]3 and [NiCN5]3 exhibit TBP and

An extensive structural study of the complexes with CN ¼ 6 has shown

Figure 15 Distortions in octahedra.

5. CRYSTAL FIELD THEORY

5.1 Ligand Field Theory (LFT)

6. SPLITTING OF d-ORBITALS IN FIELDS OF DIFFERENT

Figure 16 Shapes of ﬁve d-orbitals.

Figure 18 Splitting of d-orbitals in octahedral and tetrahedral ﬁelds.

Introduction of a tetrahedral ligand ﬁeld can be visualized by coinciding

6.1 Ligand Field Stabilization Energy (LFSE)

While LFSE in a tetrahedral ligand ﬁeld can be given as the following: