Chirality in Transition Metal Chemistry: Molecules, Supramolecular Assemblies and Materials / Edition 1

Chirality in Transition Metal Chemistry: Molecules, Supramolecular Assemblies and Materials / Edition 1

by Hani Amouri, Michel Gruselle
     
 

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ISBN-10: 0470060530

ISBN-13: 9780470060537

Pub. Date: 12/31/2008

Publisher: Wiley

Chirality in Transition Metal Chemistry shows how transition metal chirality has an important role in coordination, organometallic and supramolecular systems, and discusses applications in organic synthesis, materials science, and molecular recognition.

Overview

Chirality in Transition Metal Chemistry shows how transition metal chirality has an important role in coordination, organometallic and supramolecular systems, and discusses applications in organic synthesis, materials science, and molecular recognition.

Product Details

ISBN-13:
9780470060537
Publisher:
Wiley
Publication date:
12/31/2008
Series:
Inorganic Chemistry: A Textbook Series
Pages:
260
Product dimensions:
7.60(w) x 9.90(h) x 0.80(d)

Table of Contents

Preface ix

Foreword xi

1 Introduction 1

References 5

2 Chirality and Enantiomers 7

2.1 Chirality 7

2.1.1 Brief Historical Review 7

2.1.2 Definition of Chirality 13

2.1.3 Definition of a Prochiral Object 17

2.1.4 Definition of Elements of Chirality 19

2.1.5 Principal Elements of Chirality Encountered in Organometallic and Coordination Chemistry 20

2.2 Enantiomers and Racemic Compounds 24

2.2.1 Enantiomers 24

2.2.2 Racemic Compounds 24

2.2.3 Diastereomers 27

2.2.4 Enantiomeric and Diastereomeric Excesses 29

2.2.5 Racemization and Configurational Stability 30

2.3 Absolute configurations and System Descriptors 32

2.3.1 Definition of the Absolute and Relative Configuration of a Molecule 32

2.3.2 Absolute Configuration and Universal Descriptors 33

2.4 Physical Properties of Enantiomers and Racemics 43

2.4.1 Optical Properties 43

2.4.2 Determination of Absolute Configuration 48

2.4.3 Determination of the Enantiomeric Excess (ee) 50

2.5 Principles of Resolution and Preparation of Enantiomers 55

2.5.1 Spontaneous Resolution 55

2.5.2 Use of a Chiral Auxiliary 56

2.5.3 Chromatography 57

2.5.4 Enantioselective Synthesis 58

2.6 Summary 61

References 61

3 Some Examples of Chiral Organometallic Complexes and Asymmetric Catalysis 65

3.1 Chirality at Metal Half-sandwich Compounds 65

3.1.1 Chiral Three-legged Piano Stool: the CpMnL1L2L3 Model 65

3.1.2 Chiral Three-legged Piano Stool: the CpReL1L2L3 Model 68

3.1.3 Other Related Complexes with Chiral-at-Metal Centre 71

3.2 Chiral-at-metal Complexes in Organic Synthesis 75

3.2.1 The Chiral Acyl-Iron Complex 75

3.2.2 The Chiral Cyclic Acyl-Cobalt Complex 79

3.2.3 The LewisAcid-Rhenium Complex 79

3.3 Asymmetric Catalysis by Chiral Complexes 80

3.3.1 Asymmetric Hydrogenation 80

3.3.2 Asymmetric Epoxidation and Dihydroxylation 88

3.3.3 Gold Complexes in Asymmetric Catalysis 89

3.3.4 Asymmetric Nucleophilic Catalysis 91

3.4 Summary 94

References 94

4 Chiral Recognition in Organometallic and Coordination Compounds 99

4.1 Octahedral Metal Complexes with Helical Chirality 101

4.1.1 Heterochiral Recognition 101

4.1.2 Homochiral Recognition 102

4.1.3 Chiral Recognition Using Modified Cyclodextrins 103

4.2 Chiral Recognition Using the Chiral Anion Strategy 105

4.2.1 Tris(tetrachlorobenzenediolato) Phosphate Anion (TRISPHAT) 105

4.2.2 1,1'-binaphty1-2,2'-diyl Phosphate Anion (BNP) 111

4.2.3 Bis(binaphthol) Borate Anion (BNB) 113

4.3 Brief Introduction to DNA Discrimination by Octahedral Polypyridyl Metal Complexes 114

4.3.1 Introduction 114

4.3.2 Background on DNA Binding with Chiral Octahedral Metal Complexes- the [Ru(phen) 3]2+ Example 115

4.3.3 Molecular Light Switches for DNA 116

4.4 Summary 117

References 117

5 Chirality in Supramolecular Coordination Compounds 121

5.1 Self-assembly of Chiral Polynuclear Complexes from Achiral Building Units 121

5.1.1 Helicates 121

5.1.2 Molecular Catenanes and Knots 129

5.1.3 Chiral Tetrahedra 133

5.1.4 Chiral Anti(prism) 143

5.1.5 Chiral Octahedra and Cuboctahedra 146

5.1.6 Chiral Metallo-macrocycles with Organometallic Half-sandwich Complexes 147

5.2 Chirality Transfer in Polynuclear Complexes: Enantioselective Synthesis 153

5.2.1 Chirality Transfer via Resolved Bridging Ligands 154

5.2.2 Chirality Transfer via a Resolved Chiral Auxiliary Coordinated to a Metal or the Use of Resolved Metallo-bricks 162

5.3 Summary 172

References 172

6 Chiral Enantiopure Molecular Materials 179

6.1 General Considerations 179

6.1.1 Types of Organization 179

6.1.2 Properties 180

6.1.3 Chiral and Enantiopure Materials 180

6.2 Conductors 181

6.2.1 General Considerations 181

6.2.2 Why Enantiopure Molecular conductors? 182

6.2.3 Strategies to Obtain Enantiopure Conductors 183

6.3 Metallomesogens 189

6.3.1 General Considerations 189

6.3.2 Metallomesogens with the Chiral Element Attached Driectly to the Metal 189

6.3.3 Metallomesogens with the Chiral Element (s) in the Ligands 190

6.3.4 Metallomesogens Where the Metal and Ligands Generate Helical Chirality 193

6.3.5 Metallomesogens Based on Chiral Phthalocyanines 199

6.4 Porous Metalorganic Coordination Networks (MOCN) 204

6.4.1 General Considerations 204

6.4.2 Main Strategies to Obtain Enantiopure MOCNs 205

6.4.3 1D MOCNs 206

6.4.4 2D and 3D MOCNs 209

6.5 Molecular Magnets 215

6.5.1 Why Enantiopure Molecular Magnets? 215

6.5.2 Strategies and Synthesis 216

6.5.3 Enantioselective Synthesis or Resolution of Chiral Ligands 216

6.5.4 Chiral Inductive Effect of Resolved Building Blocks in the Formation of Supramolecular Structures 218

6.5.5 Chiral Inductive Effect of Resolved Templates 222

6.6 Chiral Surfaces 224

6.6.1 General Considerations 224

6.6.2 Spontaneous Resolution of Chiral Molecules at a Metal Surface in 2D Space 225

6.6.3 Induction of Chirality by Enantiopure Chiral Molecules in 3D, Resulting in Enantiopure Structures at Metal Surfaces 228

6.6.4 Formation of Chiral Metal Surfaces by Electrodeposition in the Presence of a Chiral Ionic Medium 229

6.6.5 Formation of Chiral Nanoparticles 229

6.7 Summary 232

References 233

Index 239

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