Molecular Metal-Metal Bonds

Systematically covering all the latest developments in the field, this is a comprehensive and handy introduction to metal-metal bonding. The chapters follow a uniform, coherent structure for a clear overview, allowing readers easy access to the information. The text covers such topics as synthesis, properties, structures, notable features, reactivity and examples of applications of the most important compounds in each group with metal-metal bonding throughout the periodic table. With its general remarks at the beginning of each chapter, this is a must-have reference for all molecular inorganic chemists, including PhD students and postdocs, as well as more experienced researchers.

Autorentext
Stephen Liddle obtained his BSc Hons (1997) and PhD (2000) from Newcastle University. After postdoctoral fellowships at Edinburgh, Newcastle, and Nottingham Universities he took up a Royal Society University Research Fellowship at Nottingham (2007) and was promoted to Associate Professor and Reader (2010). He has been awarded an ERC Starting Investigators Grant (2009, uranium-metal bonds), the RSC Sir Edward Frankland Fellowship and Bill Newton awards (2011), and he was a co-recipient of the IChemE Petronas prize for education and training (2008). He was elected as a Fellow of the Royal Society of Chemistry in 2011. He is Chairman of COST Action CM1006 and was recently elected as a Vice President of the executive committee of the European Rare Earth and Actinide Society. He is a member of the Board of Editors for Philosophical Transactions A of the Royal Society and has published over 100 primary-research and review articles to date.

Klappentext

Systematically covering all areas of the Periodic Table, this is a comprehensive and handy introduction to metal-metal bonding.

The 15 chapters follow a uniform, coherent structure for a clear overview, allowing readers easy access to the information. The important molecules at the genesis of each area are mentioned but the focus lies principally on research published since 2005. Important topics such as synthesis, properties, structures,
notable features, reactivity and examples of applications of the most important compounds in each group with metal-metal bonding throughout the periodic table are the key to this book.

With its general remarks at the beginning of each chapter, this is a must-have reference for all molecular inorganic chemists, including PhD students and postdocs, as well as more experienced researchers.

Inhalt

Preface XV

List of Contributors XVII

1 Introduction and General Survey of MetalMetal Bonds 1
John E. McGrady

1.1 Introduction 1

1.2 MetalMetal Bonds Involving s Orbitals 3

1.3 MetalMetal Bonds Involving d Orbitals 5

1.4 MetalMetal Bonds Between f Orbitals 16

1.5 MetalMetal Bonds Between p Orbitals 17

1.6 Concluding Remarks 19

References 20

2 s-Block MetalMetal Bonds 23
Cameron Jones, Philip Mountford, Andreas Stasch, and Matthew P. Blake

2.1 Introduction 23

2.2 Group 1 Bimetallics 23

2.2.1 Group 1 Diatomics and Related Species 23

2.2.2 Stable Complexes with Group 1 MetalMetal Bonding Interactions, and Related Species 25

2.2.3 Stable MetalMetal Bonded Complexes Involving One Group 1 Metal 25

2.3 Group 2 Homobimetallics 27

2.3.1 Group 2 Diatomics and Related Species 27

2.3.2 Transient Group 2 Metal(I)Metal(I) Bonded Dimers 28

2.3.3 Isolable Group 2 Metal(I)Metal(I) Bonded Dimers 29

2.4 Group 2 Heterobimetallics 34

2.4.1 Group 2Transition Metal Complexes 34

2.4.2 Group 2Main Group Metal Complexes 39

References 42

3 Group 3, Lanthanide, and Actinide MetalMetal Bonds 47
Benjamin Oelkers and Rhett Kempe

3.1 Introduction 47

3.1.1 The Isocarbonyl Problem 48

3.2 Preparation 48

3.2.1 Salt Elimination 48

3.2.2 Alkane and Amine Elimination 51

3.2.3 Reductive Cleavage of MetalMetal Bonds 54

3.2.4 Adduct Formation 57

3.3 Reactivity 59

3.3.1 Deprotonation of Acidic Substrates 60

3.3.2 Intramolecular Deprotonation and CH Activation 61

3.3.3 Oxidation of the MetalMetal Bond 62

3.4 Solid-State Structures 63

3.4.1 Typical Structures 63

3.4.2 MetalMetal Bond Lengths 64

3.5 Theoretical Calculations and Bonding 66

3.5.1 Complexes with Rare Earth Metals 66

3.5.2 Complexes with Actinide Metals 69

References 69

4 Group 4 MetalMetal Bonds 73
Lutz H. Gade

4.1 Introduction 73

4.2 Homodinuclear Group 4 Complexes: MetalMetal Bonding or Not? 73

4.3 Heterobimetallic Complexes Containing MetalMetal Bonds Involving Group 4 Metals 74

4.3.1 MetalMetal Bond Polarity in Early-Late Heterobimetallic Complexes Involving Group 4 Metals 75

4.3.2 Synthetic Strategies for the Generation of Highly Polar MetalMetal Bonds 77

4.3.3 Factors Influencing the Stability of Unsupported MetalMetal Bonds in Ti/Zr/HfM Heterodimetallic Complexes 79

4.4 Basic Patterns of Reactivity Observed for MetalMetal Bonded Early-Late Heterodinuclear Complexes 81

4.4.1 Insertions into Polar MetalMetal Bonds and Subsequent Transformations 82

4.4.2 Reactivity of Phosphinoamide-Bridged ZrCo Heterobimetallic Complexes 85

4.5 Early-Late Heterobimetallic Complexes of Group 4 Metals as Potential Catalysts 85

References 88

5 Group 5 MetalMetal Bonds 91
Sundargopal Ghosh and Dipak Kumar Roy

5.1 General Remarks 91

5.2 Vanadium Complexes 91

5.2.1 Carbonyl Complexes 92

5.2.2 Amido, Imido and Nitride Complexes 92

5.2.3 Hydride, Alkyl and Aryl Complexes 95

5.2.4 Chalcogenide Complexes 97

5.2.5 Vanadaboranes 99

5.2.6 Vanadaheteroboranes 101

5.2.7 Triple-Decker Complexes 103

5.2.8 Paddlewheel Complexes 104

5.3 Niobium Complexes 106

5.3.1 Hydride, Alkyl, and Aryl Complexes 106

5.3.2 Nitride Complexes 108

5.3.3 Triple-Decker Complexes 109

5.3.4 Paddlewheel Complexes 110

5.3.5 Niobaborane and Niobaheteroboranes 111

5.4 Tantalum Complexes 114

5.4.1 Carbonyl Complexes 114

5.4.2 Hydride, Alkyl, and Aryl Complexes 114 5.4...