FACULTY OF SCIENCE

AND

FACULTY OF ETERNAL STUDIES

BACHELOR OF EDUCATION (BED SCI)

SCH 304: INORGANIC CHEMISTRY 4

CO-ORDINATION CHEMISTRY

Written by

Dr Lydia W. Njenga
Department of chemistry

Reviewed by

Prof. Shem O Wandiga

Department of chemistry

Edited & Coordinated by:

J. O. Odumbe
Director CO &DL

-i-
SCH 304 INORGANIC CHEMISTRY 4 (COORDINATION CHEMISTRY)

COURSE OUTLINE PAGE

INTRODUCTION vii

REFERENCES viii

PERIODIC TABLE ix

LECTURE 1

INTRODUCTION OF TRANSITION ELEMENTS

1:1 Introduction 1
1:2 Electronic configurations. 2
1:3 Properties of transition elements 3
1:4 Ground state term symbols- the Russel Saunders coupling scheme 5

LECTURE 2

COORDINATION COMPOUNDS
2:1 Introduction 14
2:2 Introductions to coordination compounds 15
2:3 Types of ligands 16
2:4 Oxidation Number 18
2:5 Nomenclature 20
2:6 Evidence of coordination 21

- ii -
 2:7 Effective Atomic Number (EAN) or 18-electron rule 23

LECTURE 3

Stereochemistry
3:1 Introduction 25
3:2 Stereoisomerism 26
3:3 Geometrical isomer 26
3:4 Linkage isomers 28
3:5 Ionization isomers 29
3:6 Bridged isomers 31
3:7 Optical isomers 31

LECTURE 4

Valence Bond Theory (VBT)

4:1 Introduction 34
4:2 Assumption 34
4:3 Hybridization 35
4:4 Tetrahedral Complexes 38
4:5 Square planar 39
4:6 Failure of Valence Bond Theory 39

LECTURE 5

Crystal field Theory (CFT).

5:1 Introduction 41
5:2 Crystal field splitting for Octahedral (Oh), 41
5:3 Ground state electronic configurations d1 –d10 47
5:4 Factors affecting magnititude of ∆0 51
5:5 Splitting of d orbital of lower symmetry 57
5:6 Crystal field stabilization energies 60

- iii -
LECTURE 6

EVIDENCE FOR THE SPLITTING OF THE D ORBITALS IN CFT OR LFT

6:1 Introduction 65
6:2 Structural – Ionic radii 66
6:3 Thermodynamic factors 67

LECTURE 7

ELECTRONIC SPECTRA OF TRANSITION METAL COMPLEXES

7:1 Introduction 71
7:2 The splitting of the states 72
7:3 Origin of Color 75
7:4 Selection rules 78
7:5 Electronic spectra of some complexes 80
7:6 Microstates 82
7:7 Orgel and Tanabe – Sugano diagrams 85

LECTURE 8

ADJUSTED CRYSTAL FIELD THEORY (ACFT) OR LIGAND FIELD THEORY (LFT)

8:1 Introduction 91
8:2 Assumption 91
8:3 Spin orbit coupling 93
8:4 Interelectronic repulsion parameters 93
8:5 Nephelauxetic effect 97

- iv -
LECTURE 9

MOLECULAR ORBITAL THEORY (MOT)

9:1 Introduction 99
9:2 Formation of molecular orbitals in octahedral 100
9:3 Complexes without ∏ orbitals ( metal –ligand δ interactions). 105
9:4 Complexes with ∏ orbitals. (metal – ligand ∏ bonding) 109
9:5 Comparison of VBT and MOT 114
9:6 Comparison of CFT and MOT 114

LECTURE 10

MAGNETISM
10:1 Introduction 116
10:2 Diamagnetism 117
10:3 Paramagnetism 118

LECTURE 11

JAHN TELLER EFFECT

11:1 Introduction 126
11:2 Theorem 126
11:3 Jahn Teller Distortion effect 127
11:4 Stabilization energy 129
11:5 Effect of Jahn Teller on the spectra 130

-v-
LECTURE 12

CHARGE SPECTRA
12:1 Introduction 132
12:2 Definition 133
12:3 Intra - Ligands Transition 133
12:4 Ligand – Metal Transition 134
12:5 Metal – Ligand Transition 136
12:6 Metal – Metal Transition 137

ANSWERS TO ACTIVITY 139 -145

- vi -
 INTRODUCTION

I would like to take this opportunity to welcome you to the third year inorganic chemistry 4 on
the chemistry of coordination compounds. For this unit Knowledge of inorganic chemistry 1 and
2 will be required. In inorganic chemistry 1 you were introduced to the structure of the atom,
electronic configuration, shapes of the molecules, molecular orbital energy diagrams and the
periodic table. In inorganic chemistry 2 you covered the chemistry of the s and p block elements
of the periodic table.

During the study of this unit, we will try to broaden your knowledge on the chemistry of the
transition elements (d and f block elements) by looking at the chemistry of coordination
compounds. The study of coordination will cover the nomenclature, stereochemistry, working
out the state term symbols and bonding. Bonding will be discussed under valence bond theory,
Crystal field theory, adjusted crystal field theory and molecular field theory. To study the
properties of the coordination complexes, electronic spectra (d – d transition and charge transfer)
will be used to discuss the occurrence of different colors in complexes while magnetic moments
will be used to explain the magnetism of the compounds.

The unit has been divided into 12 lectures which will be covered within one semester. Each
lecture starts with a short introduction, objectives and followed by the discussion of the lecture.
Furthermore each lecture has worked out examples which are easy to follow. At the end of each
topic practice activities are given which you are expected to do. Answers of the activities are
given at the end of lecture 12. You are expected to do the excise first without looking at the
answers and then mark for yourself.

The course will constitute 70% of the final examination and 30% continuous assessment tests.
The materials presented in this unit are very comprehensive. However you are advised to make
reference to the following text books below. During your residential training, the aspects of the
course which you find will be explained.

- vii -
 REFERENCE

1. F.A Cotton and G. Wilkinson (1969) “ Advanced Inorganic Chemistry”, John weily and
Sons, New York

- viii -
2. S.F.A Kettle “Co-ordination compounds” Thomas Nelson and sons Ltd: 1975

3. William W. Porterfield “Inorganic chemistry. A unified approach” Addison-Wesley

Publishing company: 1984.

4. Raymond Chang “Chemistry” 4th edition, McGraw-Hill Company

5. William L. Jolly “Modern inorganic chemistry” McGraw-Hill Company

6. Satya Prakash, G. D. Tuli, S. K. Basu and R. D. Madan, 2000, “ Advanced Inorganic

Chemistry” S. Chard & company, Ram Nagar, New Delhi.

7 Any other Inorganic chemistry book

- ix -
Main Group
Elements
I II III IV
1
H
1s1
3 4 5
B 6
C
Li Be
2s 1
2s 2
2p1 2p2
11 12 Transition Elements 13
Al 14
S
Na M
3s 1
g III IV V VI VII VIII I II 3p1 3p
2
3s
19 20 21 22 23 24 25 26 27 28 29 30 31
Ga 32
G
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn
4s 1
4s 2 1
3d 4s 2
3d14s 2
3d 4s 3 2
3d 4s5 1
3d 4s5 2 6
3d 4s 2 7
3d 4s 2
3d 4s8 2
3d 4s10 1
3d 4s 10 2
4p1 4p2
37 38 39 40 41 42 43 44 45 46 47 48 49
In 50
Sn
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
5s 1
5s 2 1
4d 4s 2
3d 4s2 2
4d 5s 3 2
4d 5s5 1
4d 5s5 2 6
4d 5s 2 7
4d 5s 2
4d 5s8 2
4d 5s10 1
4d105s2 5p1 5p2
55 56 57 72 73 74 75 76 77 78 79 8 0 81
Tl 82
Pb
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg
6s 1
6s 2 1
5d 6s 2 2
5d 4f 6s 14 2 2
5d 4f 6s 14 2 2
5d 4f 6s 14 2 2
5d 4f 6s 14 2 2
5d 4f 6s 14 2 2
5d 4f 6s 14 2 9
5d 4f 6s 14 1 10
5d 4f 6s 14 1
5d 2 4f 1 4 6s 2 6p1 6p2
87 88 89 104 105 106 107
Fr Ra Ac Rf Ha
1 2 2 14 2 2 14 2 2 14 2 2 14 2
7s 7s 6d 5f 7s 6d 5f 7s 65d 5f 7s 6d 5f 7s 6d25f147s2

58 59 60 61 622 63 64 65 66 67 68
Lanthanide Elements Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho
0 1 2 0 34 2 0 4 2 0 5 2 0 6 2 0 7 2 0 8 2 0 9 2 0 10 2 2 11 2
5d 4f2 6s 5d 4f 6s 5d 4f 6s 5d 4f 6s 5d 4f 6s 5d 4f 6s 5d 4f 6s 5d 4f 6s 5d 4f 6s 5d 4f 6s 5d2
90 91 92 93 94 95 96 97 98 99 10
Actinide Elements Th Pa U Np Pu Am Cm Bk Cf Es
2 o 2 1 2 2 1 3 2 1 4 2 0 6 2 0 7 2 1 7 2 0 9 2 0 10 2 0 11 2
6d 5f 7s 6d 5f 7s 6d 5f 7s 6d 5f 7s 6d 5f 7s 6d 5f 7s 6d 5f 7s 6d 5f 7s 6d 5f 7s 6d 5f 7s 6d0

- 10 -