Coordination Chemistry: Metal Complexes

Coordination Chemistry: Metal Complexes

by P. L. Soni, Vandna Soni

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Product Details

ISBN-13: 9781466500501
Publisher: Ane Books
Publication date: 04/30/2013
Pages: 300
Product dimensions: 6.60(w) x 9.70(h) x 0.90(d)

Table of Contents

Part I Coordination Chemistry (Metal Complexes)

1 Historical Background 3

1.1 Complexes 3

1.2 Difference between Double Salts and Complex Substances 4

Summary 4

2 Introduction 5

2.1 Coordination Sphere 5

2.2 Formation of a Complex 6

2.3 Bridging Ligands 8

2.3.1 Non-Chelates 12

2.3.2 Chelates 12

Summary 15

3 Correct Empirical Formula of Complexes 17

3.1 Precipitation Method 17

3.2 Molar Conductivity Method 18

3.3 Effective Atomic Number (EAN Rule) 19

3.4 Blomstrand-Jorgensen Chain Theory 20

3.5 Werner's Coordination Theory 21

Summary 24

4 IUPAC Nomenclature 27

4.1 Nomenclature of Coordination Compounds 27

4.2 General Rules 27

4.3 Naming the Metal Ion 27

4.4 Naming the Ligand 28

Summary 33

5 Isomerism and Stereochemistry 35

5.1 Isomerism 35

5.2 Structural Isomerism 35

5.3 Stereoisomerism 39

Summary 50

6 Bonding in Complexes 53

6.1 Nature of Metal-ligand Bond 53

6.2 Lewis Acid-base Theory 53

6.3 Valence Bond Theory 54

6.4 Crystal Field Theory (CFT) 62

6.5 Ligand Field Theory (LET) 76

Summary 83

7 Preparation and Isolation of Complexes 87

7.1 Preparation 87

7.2 Isolation 90

Summary 91

8 Stability of Complex Ion 93

8.1 Introduction 93

8.2 Factors Influencing Stability 94

Summary 96

9 Kinetics or Inert and Labile Complexes 99

9.1 Introduction 99

9.2 Inert and Labile Complexes 101

9.2.1 Classification of Inert and Labile Complexes on the Basis of Electrons in d Orbitals 102

9.2.2 Inert and Labile on the Basis of CFSE 102

9.2.3 Role of a Catalyst (Kinetics) 103

Summary 105

10 Substitution Reactions in Complexes 109

10.1 Introduction 109

10.2 Mechanism of Substitution 110

10.3 Substitution in Non-aqueous Solvents 111

10.4 Substitution when no Solvent is Used 112

10.5 Mechanisms of Substitution 113

Summary 114

Select Topics

11 Metal Carbonyls and Nitrosyls 119

11.1 Introduction 119

11.2 Preparation of Metal Carbonyls 120

11.3 Structure and Bonding in Carbonyls 123

11.4 Iron I Pentacarbanyl [Fe(CO)5] 125

11.5 Polynuclear Metal Carbonyls 130

11.6 Dicobalt Octacarbonyl [Co2(CO)8] 133

Summary 142

Organometallics

12 Organometallics 149

12.1 Introduction 149

12.2 Definition 149

12.3 Classification 150

12.4 Nomenclature 150

12.5 Synthesis of Organometallic Compounds 152

12.6 Metal-Alkene Complexes of π-Bonded Organometallics 163

12.7 Sandwich Organometallics or Metallocenes 165

12.8 Molecular Orbital Theory (MOT) 171

Summary 174

Part II Coordination Chemistry (Transition Metal Chemistry)

1 General Characteristics of d-block Elements 3

1.1 Introduction 3

1.2 Placement in the Periodic Table 5

1.2.1 Electronic Configuration 6

1.2.2 Second Transition Series (4rf-series) 7

1.2.3 Third Transition Series or 5d-series 8

1.2.4 Fourth Transition Sereis or 6d-sereis 8

1.2.5 Electronic Configuration of Transition Metal Ions 9

1.2.6 Atomic and Ionic Radii 10

1.2.7 Metallic Behaviour 11

1.2.8 Atomic Volume and Density 11

1.2.9 Melting and Boiling Points 12

1.2.10 Variable Oxidation States 13

1.2.11 Ionisation Energies 15

1.2.12 Reducing Action 16

1.2.13 Colour of Transition Metal Ions 18

1.2.14 Magnetic Properties 20

1.2.15 Diamagnetism 23

1.2.16 Ferromagnetism 23

1.2.17 Antiferromagnetism 23

1.2.18 Complex Formation Tendency 24

1.2.19 Stability of Complex Compounds 24

1.2.20 Catalytic Property 25

1.2.21 Interstitial Compound 26

1.2.22 Alloy Formation 27

1.2.23 Reactivity 27

1.3 Group Study of Physical and Chemical Characteristics of Transition Elements 28

1.3.1 Scandium Group 28

1.4 Physical Characteristics 29

1.4.1 Occurrence 29

1.4.2 Atomic Size 29

1.5 Chemical Characteristics 29

1.5.1 Electronic Configuration 30

1.5.2 Oxidation States 30

1.5.3 Halides 31

1.5.4 Complexes 31

2 Titanium Group 33

2.1 Introduction 33

2.2 Physical Characteristics 33

2.2.1 Electronic Configuration 33

2.2.2 Oxidation States 33

2.2.3 Extraction of Metals 34

2.2.4 Physical Constants 34

2.2.5 Atomic Size 35

2.3 Chemical Characteristics 35

2.3.1 Reactivity and Passivity 35

2.3.2 Behaviour of Ti group Compounds in Different Oxidation States 36

2.3.3 Halides 38

2.3.4 Organometallic Compounds 39

3 Vanadium Group 41

3.1 Introduction 41

3.2 Physical Characteristics 41

3.2.1 Occurrence and Extraction 41

3.2.2 Electronic Configuration and Oxidation States 42

3.2.3 Atomic Size 42

3.2.4 Graded General Properties 42

3.3 Compounds of V, Nb and Ta 44

3.3.1 Halides 44

3.3.2 Oxides 46

3.3.3 Vanadates 47

3.3.4 Organometallic Compounds 48

4 Chromium Group 49

4.1 Introduction 49

4.2 Physical Characteristics 49

4.2.1 Abundance, Occurrence and Extraction 49

4.2.2 Electronic Configuration and Oxidation States 50

4.2.3 Oxidation States 50

4.3 General Chracteristics 51

4.3.1 Compounds in (+6) State 53

4.3.2 Chromium trioxide or Chromic anhydride 54

4.3.3 Halides 55

4.3.4 Zero (-1) and (-11) State Compounds 58

4.3.5 Chromates, Molybedates and Tungstates 59

4.3.6 Tungsten Bronzes 60

4.4 The Manganese Group 60

4.4.1 Electronic Configuration and Oxidation States 60

4.4.2 Occurrence and Uses 60

4.4.3 Oxidation States 61

4.5 General Characteristics 62

4.5.1 Mn(III) Oxidation State Compounds 65

4.5.2 Mn(III) Complexes 65

4.5.3 +IV Oxidation State Compounds 66

4.5.4 +V State Compounds 67

4.5.5 +VI State Compounds 68

4.5.6 +VII State Compounds 68

4.5.7 Biological Use 69

4.6 The Iron Group 69

4.6.1 Electronic Structures and Oxidation States 69

4.6.2 Occurrence and Extraction 70

4.6.3 Steel Manufacture 72

4.6.4 Bessemer Process 72

4.6.5 Common Oxidation States 73

4.7 General Characteristics 73

4.7.1 Low Oxidation State Compounds 74

4.7.2 [Fe(CO)5] 75

4.7.3 +II Oxidation State Compounds 76

4.7.4 Oxides 76

4.7.5 Halides 77

4.7.6 Complexes 77

4.7.7 Test for NO3- or NO2- 78

4.7.8 Compounds with Oxidation State (III) 79

4.7.9 Oxides 79

4.7.10 Halides 79

4.7.11 Complexes 81

4.7.12 Cyclopentadienyl Compounds 83

4.7.13 Bioinorganic Chemistry of Iron 84

5 The Cobalt Group 87

5.1 Introduction 87

5.1.1 Compounds of (+I) State 92

5.1.2 Compounds with (+II) State 92

5.1.3 Compounds of (+III) Oxidation State 95

5.1.4 Compounds with (+IV) Oxidation State 96

5.2 The Nickel Group 97

5.2.1 Occurrence and Extraction 98

5.2.2 Common Oxidation States 99

5.3 General Properties 99

5.3.1 Compounds with Oxidation States (-I), O, (+I) 100

5.3.2 Compounds with (+II) State 101

5.3.3 Compounds with (+III) Oxidation State 103

5.3.4 Compounds of (+IV) Oxidation States 103

5.3.5 Compounds with (+V) and (+VI) States 104

5.4 The Copper Group of Coinage Metals 104

5.4.1 Abundance and Extraction 105

5.5 General Properties 107

5.5.1 Compounds in (+I) Oxidation State 108

5.5.2 Use of Ag Compounds in Photography 110

5.5.3 Compounds with (+II) Oxidation State 111

5.5.4 Compounds in (+III) Oxidation States 113

5.5.5 Compounds in (+V) State 113

5.5.6 Biological Use of Copper 113

6 The Zinc Group 115

6.1 Introduction 115

6.1.1 Occurrence 115

6.1.2 Extraction 116

6.1.3 Uses of Zinc, Cadmium and Mercury 117

6.1.4 Important and Common Oxidation States 117

6.1.5 Ionic Size and Some Physical Properties 118

6.2 General Characteristics 118

6.2.1 Oxides 120

6.2.2 Complexes 121

6.2.3 Mercury (+I) Compounds 121

6.2.4 Organometallic Compounds 122

6.2.5 Biological Role of Zn 123

6.2.6 Toxic Nature of Cd and Hg 123

7 Inner Transition of f-block Elements: The Lanthanides 131

7.1 Introduction 131

7.1.1 The Electronic Configuration 131

7.1.2 Abundance and Isotopes 132

7.1.3 Extraction 133

7.1.4 Lanthanide Contraction 136

7.1.5 Properties of (+III) Compounds 137

7.1.6 Compounds with (+IV) Oxidation State 139

7.1.7 Compounds of (+II) Oxidation State 139

7.1.8 Solubility 140

7.1.9 Colour and Spectra 140

7.1.10 Magnetic Moment 141

7.1.11 Coordination Complexes 143

8 The Actinides 147

8.1 Introduction 147

8.1.1 Electronic Configuration 148

8.1.2 Important Oxidation States 149

8.1.3 Occurrence 150

8.1.4 Preparation of Transuranium Elements 150

8.2 General Characteristics 152

8.2.1 Thorium, Protactinium and Uranuim 152

8.2.2 Chemical Characteristics 154

8.2.3 Neptunium, Plutonuim and Americium 156

8.3 Completing and Extending the Periodic Table and its Series 158

Bibliophile 161

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