Contents
The Authors vii
Preface ix
Periodic Table x
1. Introduction and Historical Development 1
1.1 Introduction 1
1.2 Historical development 2
1.3 Nomenclature 9
Problems 15
2. The Coordinate Bond 17
2.1 The electron-pair bond 17
2.2 Electronic structure of the atom 19
2.3 The concept of effective atomic number 23
2.4 Valence bond theory 25
2.5 Crystal field theory 26
2.6 Molecular orbital theory 37
Problems 43
3. Stereochemistry 45
3.1 Geometry of coordination compounds 45
3.2 Complexes with unusual structural features 49
3.3 Isomerism in metal complexes 52
, Problems 61
4. Preparations and Reactions of Coordination Compounds 63
4.1 Substitution reactions in aqueous solution 64
4.2 Substitution reactions in nonaqueous solvents 65
4.3 Substitution reactions in the absence of solvents 66
4.4 Thermal dissociation of solid complexes 67
vi Contents
4.5 Photochemical synthesis 68
4.6 Oxidation–reduction reactions 69
4.7 Catalysis 70
4.8 Substitution reactions without metal–ligand bond cleavage 72
4.9 Trans effect 74
4.10 Synthesis of cis–trans isomers 75
4.11 Preparation of optically-active compounds 77
Problems 78
5. Complex Ion Stability 80
5.1 Stability constants 82
5.2 Factors that influence complex stability 83
5.3 Stabilization of unusual oxidation states by coordination 92
5.4 Determination of stability constants 93
Problems 95
6. Kinetics and Mechanisms of Reactions of Coordination Compounds
97
6.1 Rate of a reaction 98
,6.2 The rate law 99
6.3 Effective collisions 101
6.4 Inert and labile complexes 103
6.5 Mechanisms of substitution reactions 106
6.6 Octahedral substitution reactions 107
6.7 Square planar substitution 111
6.8 Mechanisms for redox reactions114
Problems 118
7. Organometallic Chemistry and Current Research Topics 120
7.1 Preparation of metal carbonyls and organometallic compounds 120
7.2 Organometallic reactions and homogeneous catalysis 128
7.3 Metals in living systems 131
7.4 Solid state chemistry 134
Problems 136
Index of Complexes 138
Index 140
The authors
, Fred Basolo has been Professor of Chemistry at Northwestern University since
1946 and is currently Morrison Professor of Chemistry. President of the
American Chemical Society in 1982, member of the National Academy of
Sciences, he is the author of over 300 scientific publications and has co-
authored Mechanisms of Inorganic Reactions with R. G. Pearson. He has also
edited and co-edited four other volumes in inorganic chemistry. The first edition
of Coordination Chemistry has been translated into eight languages, including
Japanese and Chinese.
Ronald C. Johnson is Professor of Chemistry at Emory University in Atlanta,
Georgia where he has been on the faculty since 1961, he is a former President of
the Georgia Academy of Science and has published both research papers and
articles in the Journal of Chemical Education. Dr Johnson is author of
Introductory Descriptive Chemistry and co-author with R. A. Day of General
Chemistry.
The Authors vii
Preface ix
Periodic Table x
1. Introduction and Historical Development 1
1.1 Introduction 1
1.2 Historical development 2
1.3 Nomenclature 9
Problems 15
2. The Coordinate Bond 17
2.1 The electron-pair bond 17
2.2 Electronic structure of the atom 19
2.3 The concept of effective atomic number 23
2.4 Valence bond theory 25
2.5 Crystal field theory 26
2.6 Molecular orbital theory 37
Problems 43
3. Stereochemistry 45
3.1 Geometry of coordination compounds 45
3.2 Complexes with unusual structural features 49
3.3 Isomerism in metal complexes 52
, Problems 61
4. Preparations and Reactions of Coordination Compounds 63
4.1 Substitution reactions in aqueous solution 64
4.2 Substitution reactions in nonaqueous solvents 65
4.3 Substitution reactions in the absence of solvents 66
4.4 Thermal dissociation of solid complexes 67
vi Contents
4.5 Photochemical synthesis 68
4.6 Oxidation–reduction reactions 69
4.7 Catalysis 70
4.8 Substitution reactions without metal–ligand bond cleavage 72
4.9 Trans effect 74
4.10 Synthesis of cis–trans isomers 75
4.11 Preparation of optically-active compounds 77
Problems 78
5. Complex Ion Stability 80
5.1 Stability constants 82
5.2 Factors that influence complex stability 83
5.3 Stabilization of unusual oxidation states by coordination 92
5.4 Determination of stability constants 93
Problems 95
6. Kinetics and Mechanisms of Reactions of Coordination Compounds
97
6.1 Rate of a reaction 98
,6.2 The rate law 99
6.3 Effective collisions 101
6.4 Inert and labile complexes 103
6.5 Mechanisms of substitution reactions 106
6.6 Octahedral substitution reactions 107
6.7 Square planar substitution 111
6.8 Mechanisms for redox reactions114
Problems 118
7. Organometallic Chemistry and Current Research Topics 120
7.1 Preparation of metal carbonyls and organometallic compounds 120
7.2 Organometallic reactions and homogeneous catalysis 128
7.3 Metals in living systems 131
7.4 Solid state chemistry 134
Problems 136
Index of Complexes 138
Index 140
The authors
, Fred Basolo has been Professor of Chemistry at Northwestern University since
1946 and is currently Morrison Professor of Chemistry. President of the
American Chemical Society in 1982, member of the National Academy of
Sciences, he is the author of over 300 scientific publications and has co-
authored Mechanisms of Inorganic Reactions with R. G. Pearson. He has also
edited and co-edited four other volumes in inorganic chemistry. The first edition
of Coordination Chemistry has been translated into eight languages, including
Japanese and Chinese.
Ronald C. Johnson is Professor of Chemistry at Emory University in Atlanta,
Georgia where he has been on the faculty since 1961, he is a former President of
the Georgia Academy of Science and has published both research papers and
articles in the Journal of Chemical Education. Dr Johnson is author of
Introductory Descriptive Chemistry and co-author with R. A. Day of General
Chemistry.
