CH 5.

Transition Metals and Coordination Compounds

 Introduction:  Transition Metals
 coordination compounds

 Nomenclature of coordination compounds

 Coordination geometry and Isomerism
 Introduction
Why Study Chemistry of Transition Metals?
To understand the uses of transition metals and their compounds
 Transition metals and their compounds have many useful applications
 Fe is used to make steel and stainless steel
 Ti is used to make lightweight alloys
 Transition metal compounds are used as pigments
 TiO2 = white
 PbCrO4 = yellow

 The color of gemstones is due to the presence of transition metal ions

 Sapphires are blue due to presence of Fe and Ti

 Many biomolecules contain transition metals

 Vitamin B12 contains Co
 Coordination compound are used in many industrial processes
 Introduction

Coordination compounds

Transition metals have incompletely filled d subshells 3

 Introduction
General Properties of Transition Metals:

 Almost all are hard, strong, high mpts & bpts Metals
 Conduct heat & electricity
 Form alloys
 Many transition metal compounds are Paramagnetic
 Their compounds are colored.
 Form coordination compounds (complexes)
 Transition metal compounds act as catalysts
 They exhibit variable oxidation states

4
 Electronic Configurations
Their outer electronic structures involves d-orbitals

Element [Ar] = 1s22s22p63s23p6 Configuration

Sc [Ar]4s23d1
Ti [Ar]4s23d2
V [Ar]4s23d3
Cr [Ar]4s13d5
Mn [Ar]4s23d5
 Electronic Configurations
Element Configuration
Fe [Ar] = 1s22s22p63s23p6 [Ar] 3d64s2
Co [Ar] 3d74s2
Ni [Ar] 3d84s2
Cu [Ar]3d104s1
Zn [Ar]3d104s2
Transition Metals show Variable Oxidation States
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+1
+2 +2 +2 +2 +2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4 +4 +4
+5 +5 +5 +5
+6 +6 +6
+7
 Oxidation States of Transition Elements

Sc Ti V Cr Mn Fe Co Ni Cu Zn
+1 +1
+2 +2 +2 +2 +2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4 +4 +4
+5 +5 +5 +5
+6 +6 +6
+7
3/7/01 Ch. 24 11

loss of ns e-s
loss of ns and (n-1)d e-s
Electronic Configurations of Transition Metal Ions

• Electronic configuration of Fe2+

Electronic Configurations of Transition Metal Ions

• Electronic configuration of Fe2+

Fe – 2e-  Fe2+
Electronic Configurations of Transition Metal Ions

• Electronic configuration of Fe2+

Fe – 2e-  Fe2+
[Ar]3d64s2

valence ns e-’s removed

first
Electronic Configurations of Transition Metal Ions

• Electronic configuration of Fe2+

Fe – 2e-  Fe2+
[Ar]3d64s2 [Ar]3d6

valence ns e-’s removed

first
Electronic Configurations of Transition Metal Ions

• Electronic configuration of Fe3+

Electronic Configurations of Transition Metal Ions

• Electronic configuration of Fe3+

Fe – 3e-  Fe3+
Electronic Configurations of Transition Metal Ions

• Electronic configuration of Fe3+

Fe – 3e-  Fe3+
[Ar]3d64s2

valence ns e-’s removed

first, then n-1 d e-’s
Electronic Configurations of Transition Metal Ions

• Electronic configuration of Fe3+

Fe – 3e-  Fe3+
[Ar]3d64s2 [Ar]3d5

valence ns e-’s removed first,

then n-1 d e-’s
Electronic Configurations of Transition Metal Ions

• Electronic configuration of Co3+

Electronic Configurations of Transition Metal Ions

• Electronic configuration of Co3+

Co – 3e-  Co3+
Electronic Configurations of Transition Metal Ions

• Electronic configuration of Co3+

Co – 3e-  Co3+
[Ar]3d74s2

valence ns e-’s removed first,

then n-1 d e-’s
Electronic Configurations of Transition Metal Ions

• Electronic configuration of Co3+

Co – 3e-  Co3+
[Ar]3d74s2 [Ar]3d6

valence ns e-’s removed first,

then n-1 d e-’s
Electronic Configurations of Transition Metal Ions

• Electronic configuration of Mn4+

Electronic Configurations of Transition Metal Ions

• Electronic configuration of Mn4+

Mn – 4e-  Mn4+
Electronic Configurations of Transition Metal Ions

• Electronic configuration of Mn4+

Mn – 4e-  Mn4+
[Ar]3d54s2

valence ns e-’s removed first,

then n-1 d e-’s
Electronic Configurations of Transition Metal Ions

• Electronic configuration of Mn4+

Mn – 4e-  Mn4+
[Ar]3d54s2 [Ar]3d3

valence ns e-’s removed first,

then n-1 d e-’s
 Introduction
Other Properties of Transition Metals:

24
 Coordination Chemistry
• Transition metals act as Lewis acids
Form complexes/complex ions (Coordination compounds)
Fe3+(aq) + 6CN-(aq)  Fe(CN)63-(aq)
Lewis acid Lewis base Complex ion

Ni2+(aq) + 6NH3(aq)  Ni(NH3)62+(aq)

Lewis acid Lewis base Complex ion
Complex contains central metal ion bonded to one or more
molecules or anions
Lewis acid: is metal ion at the center of coordination
Lewis base: is a ligand, that is molecules/ions covalently bonded to
metal in complex

Ligands are molecules or ions that donate lone pairs of electrons

to form the coordinate covalent bonds
 Coordination Chemistry
Coordination Compound is a compound in which a central
metal ion is attached to a group of surrounding molecules or
ions by coordinate covalent bonds.
A transition metal forms a complex with a well defined number of
ligands called its coordination number;
[Cr(NH3)6]3+ has a coordination number of 6.

Coordination number is the number of ligand atoms bonded directly

to the central metal ion

Complexes with coordination numbers two, four and six are the common one.

1. [Ag(NH3)2]+ (2) 2. [Cu(NH3)4]+2 (4) 3. [Fe(CN)6]-3 (6)

 Common Geometries of Complex Ions

Coordination number is for example is determined by the nature of ligands.

Larger ligands and those that transfer substantial negative charge to metal
favor lower coordination numbers
The geometry of a given complex ion depends both on the
coordination number and the metal ion.

Coordination Numbers and Shapes of Some Complex Ions

Coordination
Number Shape Examples

2 Linear [CuCl2]-, [Ag(NH3)2]+, [AuCl2]-

4 Square planar [Ni(CN)4]2-, [PdCl4]2-,

[Pt(NH3)4]2+, [Cu(NH3)4]2+

4 Tetrahedral [Cu(CN)4]3-, [Zn(NH3)4]2+,

[CdCl4]2-. [MnCl4]2-

6 Octahedral [Ti(H2O)6]3+, [V(CN)6]4-,

[Cr(NH3)4Cl2]+, [Mn((H2O6]2+,
[FeCl6]3-, [Co(en)3]3+

[PbEDTA]-2 ?
Representations of [Pb(EDTA)]2

of [P)]

EDTA
Complex charge = sum of charges on the metal and the ligands

[Fe(CN)6]3-
Complex charge = sum of charges on the metal and the ligands

[Fe(CN)6]3-

+3 6(-1)
 Neutral charge of coordination compound = sum of
charges on metal, ligands, and counterbalancing ions

[Co(NH3)6]Cl2

neutral compound
 Neutral charge of coordination compound = sum of
charges on metal, ligands, and counterbalancing ions

[Co(NH3)6]Cl2

+2 6(0) 2(-1)
 Components of Coordination Compounds
The complex ion is associated with counter ions of opposite charge.

A coordination compound contains at least one complex ion, which

consists of a central metal cation bonded to molecules and/or anions
called ligands.
 Components of Coordination Compounds

The complex ion [Co(NH3)6]3+ behaves like a polyatomic ion in solution

[Co(NH3)6]Cl3 dissolves in water. The six ligands remain bound to the

complex ion.
 Types of Ligands
The ligands of a complex ion are molecules or anions with one
or more donor atoms. E.g. NH3, CN-, H2O
Donor atom: the atom in a ligand that is bound directly to the
metal atom , has lone electron pairs. E.g. C, N, O, S, F, Cl, Br, I

Each donor atom donates a lone pair of electrons to the metal ion
to form a coordinate covalent bond.

Depending on the number of donor atoms present in the molecule

or ion, ligands can be classified as Monodentate & Polydentate.
1.Monodentate ligands: coordinated to the central metal ion
through a lone pair electrons on a single atom anion.
Monodentate : (H2O: :NH3)
 Types of Ligands
2.Polydentate ligands bound to the central metal ion through two or more lone
pair electrons, which are resting on separate atoms of the same ligand groups

Polydentate ligands are commonly referred to as chelates (chelating ligands).

Bidentate ：（H2N-CH2-CH2-NH2） Hexadentate： (EDTA)

Low oxidation state metal ion complexes can be stabilized by using

ligands such as cyanide and carbon monoxide (-acceptor ligands);

Intermediate oxidation states metal ion complexes often have ligands

such as ammonia or water;

High oxidation state metal ion complexes usually have fluoride or

oxides as ligands.
Structure of Some common chelating ligands

glycinato
Example of Common Monodentate Ligands

Examples of Common Polydentate Ligands

39
 Naming of Coordination compounds
According to International Union of Pure and Applied Chemistry
(IUPAC), based on the follwing Rules

1. The cation is named before the anion.

NaCl: sodium choride
2. Within a complex ion the ligands are named first, in
alphabetical order, and the metal ion is
named last.
3. To name the ligands:
anionic ligands end in -o
neutral ligands usually called the name of the molecule
Naming of Coordination compounds
LIGANDS Name of Ligand in Coord.
Cpd.
Bromide, Br- Bromo
Chloride, Cl- Chloro
Cyanide, CN- Cyano
Hydorxide, OH- Hydroxo
Oixde, O2- Oxo
Carbonate, CO32- Carbanato
Nitrite, NO3- Nitro
Oxolate, C2O42- Oxolato
Ammonia, NH3 Ammine
Carbon monoxide, CO Carbonyl
Water, H2O Aquo
Ethylenediamine(en) Ethylenediamine
 Naming of Coordination compounds
4.When several ligands of a particular kind are present, we
use the Greek prefixes to name them.
• Di (2)
• tri (3)
[Co(NH3)4Cl2]+ is
• tetra (4) tetraamminedichloro
• Penta (5)
• Hexa (6)

If the ligand itself contains a Greek prefix, we use the prefixes

bis, tris, tetrakis to indicate the number of ligands present.

E.g. Two NH2CH2CH2NH2 ligands named as bis-ethylenediamine;

Two HOOC-COOH ligands as bis-oxalato- etc.,

[Cu(en)2]2+ is named bis(ethylenediamine)

 Naming of Coordination compounds
5. After the ligands names in the complex, the name of the metal
followed by its oxidation state (in Roman numeral) will be written;
 However, in case of anionic complexes, the name of the metal ion
will be modified and the suffix-‘ate’ will be added.
 In case of neutral and cationic complexes, the name of the metal
remain the same

Examples:
[PtVI Cl2(NH3)2]2+ …..is named as dichlorodiammineplatinium(IV);
[NiII (NH3)4]2+ ….. is named as tetraaminnenickel(II)
[CrIII (H2O)6]3+ ….. is named as hexaaquochromium(III)
[FeIII (Ox)3]3- .…. is named as trisoxalatoferrate(III)
[Ni0(CO)4] ….. is named as tetracarbonylnickel(0)
 Naming of Coordination compounds

Transition Name if in Cationic Name if in Anionic Complex

Metals Complex
Sc Scandium Scandate
Ti titanium titanate
V vanadium vanadate
Cr chromium chromate
Mn manganese manganate
Fe iron ferrate
Co cobalt cobaltate
Ni nickel nickelate
Cu Copper cuprate
Zn Zinc zincate
 Examples
1. Give the Formula for the following coordination compounds.
A. Tetracarbonylnickel(0)
Ni(CO)4,
B. Tetraammineaquochlorocobalt(III) chloride
[Co(NH3)4H2OCl]Cl2

How did I know there had to be two chlorides at the end?

2. Write the correct Name for the following coordination compounds.

A. [CrCl(H2O)5]Cl2.H2O
Pentaaquochlorochromium(III)chloridemonohydrate
B. K4[Fe(CN)6]
Potassiumhexacyanoferrate(II)
 Exercise
1. Write the Name of the following coordination complexes

a) [Cr(NH3)4Cl2]+ d) K4[Fe(CN)6]

b) [Co(NH3)4(Cl)2]Cl e) [Fe(CO)5]

c) K3[Fe(CN)6] f) [Cr(en)3]Cl3

2. Determine the oxidation numbers of the central metal in the

complexes above

46
Isomerism in Coordination Compounds

47
 Isomerism in Coordination Compounds
Isomers are compounds with the same chemical formula
but different structures

As they have different structures, they will have different properties

Coordination Compounds

Structural
Isomers Stereo Isomers
(different bonds) (identical
bonds)
Linkage Hydration
Isomers Isomers Geometric Optical
Ionization Coordination Isomers Isomers
Isomers /Postion
Isomers
48
 Structural Isomers

Hydration isomers:

Water in outer sphere, this is part of solvent)

Water in the inner sphere. It is a ligand

in the coordination sphere of the metal

[Cr(H2O)6]Cl3 [CrCl(H2O)5]Cl2.H2O [CrCl2(H2O)4]Cl.2H2O

Violet Green Dark green
 Structural Isomers
Linkage isomers
Exhibited with ligands having 2 or more bonding atoms
Examples: SCN, NO2
NO2 can be bonding to metal at the N or the O atom

Bonding occurs from Bonding occurs from

N atom to metal O atom to metal

[Co(NH3)5NO2]Cl2 [Co(NH3)5ONO]Cl2
 Structural Isomers
Ionization isomers
Same formula but due to differences in outer/inner sphere
ions
[CoBr(NH3)5]SO4 [CoSO4 (NH3)5]Br

Coordination isomers
[Co(NH3)6][Cr(CN)6] & [Co(CN)6][Cr(NH3)6]

[Cr(NH3)6][Cr(CN)6] & [Cr(NH3)4 (CN)2[Cr(CN)

] 4(NH3)2]

Coordination position isomers

Exhibited by bridged complexes
OH OH 2+
2+

(NH3)4Co Co(NH3)2(Cl)2 & Cl(NH3)3Co Co(NH3)2Cl

OH OH
 Stereoisomers
Compounds that have the same chemical formula and bonds
but they have different spatial arrangement.

 Ligands arranged differently and thus distinctly different properties

Geometric isomers: Designated as cis and trans

cannot be interconverted without breaking chemical bonds

Cis and Trans Isomers of Diamminedichloroplatinum(II)

 Stereoisomers
Optical isomers: If a molecule possess a plane of symmetry it is
achiral & is superimposible on its mirror image. Optical Isomers
(Enantiomers) NOT possible

Enantiomers are mirror images which are not superimposable, & do not
have a plane of symmetry: Chiral (optical isomers possible)
Enantiomers rotate polarized light in different directions; they are termed
“optical isomers”

(b)
 Stereoisomers:
Optical isomers (Enantiomers)

Plane of symmetry No plane of symmetry

Achiral (one structure) Chiral (two enantiomer)
 Stereoisomers:
Optical isomers (Enantiomers)
Which of the following Cobalt complexes show Optical Isomers
 Optical Isomers of Geometric Isomers

cis trans
rotate in any manner rotate 90o
nonsuperimposable superimposable
chiral achiral
Polarimetry
 Bonding Theories in TM Complexes
 Alfred Werner – 1893
The Nobel Prize in Chemistry 1913 "in recognition
of his work on the linkage of atoms in molecules
by which he has thrown new light on earlier
investigations and opened up new fields of
research especially in inorganic chemistry”
 Valance Bond Theory
Linus Carl Pauling
Basic Principle Nobel prizes: 1954, 1962
A covalent bond forms when the orbtials of
two atoms overlap & are occupied by a pair
of electrons that have the highest probability
of being located between the nuclei.

Ligand = Lewis base

Examples:

Metal = Lewis acid

(1901-1994)
Examples:

M L Coordinate covalent bond