Transition Metal-Dinitrogen Complexes

A comprehensive book that explores nitrogen fixation by using transition metal-dinitrogen complexes Nitrogen fixation is one of the most prominent fields of research in chemistry. This book puts the focus on the development of catalytic ammonia formation from nitrogen gas under ambient reaction conditions that has been recently repowered by some research groups. With contributions from noted experts in the field, Transition Metal-Dinitrogen Complexes offers an important guide and comprehensive resource to the most recent research and developments on the topic of nitrogen fixation by using transition metal-dinitrogen. The book is filled with the information needed to understand the synthesis of transition metal-dinitrogen complexes and their reactivity. This important book: -Offers a resource for understanding nitrogen fixation chemistry that is essential for explosives, pharmaceuticals, dyes, and all forms of life -Includes the information needed for anyone interested in the field of nitrogen fixation by using transition metal-dinitrogen complexes -Contains state-of-the-art research on synthesis of transition metal-dinitrogen complexes and their reactivity in nitrogen fixation -Incorporates contributions from well-known specialists and experts with an editor who is an innovator in the field of dinitrogen chemistry Written for chemists and scientists with an interest in nitrogen fixation, Transition Metal-Dinitrogen Complexes is a must-have resource to the burgeoning field of nitrogen fixation by using transition metal-dinitrogen complexes.

Auteur

Yoshiaki Nishibayashi is a full professor at The University of Tokyo. The award-winning professor's current research interests focus on organic and organometallic chemistry. He is the author of more than 200 publications and review articles.

Contenu
Preface xi

About the Editor xiii

1 Overviews of the Preparation and Reactivity of Transition MetalDinitrogen Complexes 1
*Yoshiaki Tanabe and Yoshiaki Nishibayashi*

1.1 Introduction 1

1.2 Biological Nitrogen Fixation 4

1.3 Historical Background of Transition MetalDinitrogen Complexes 9

1.4 Coordination Chemistry of Transition MetalDinitrogen Complexes 13

1.4.1 Coordination Patterns of Dinitrogen and Mononuclear Transition MetalDinitrogen Complexes 13

1.4.2 Multinuclear Transition MetalDinitrogen Complexes 16

1.5 Chemical Activation and Reactivity of Dinitrogen Using Transition Metal Complexes 21

1.5.1 Protonation of Transition Metal-bound Dinitrogen 21

1.5.2 Cleavage of Transition Metal-bound Dinitrogen 25

1.5.3 Reaction of Transition Metal-bound Dinitrogen with Dihydrogen 26

1.5.4 Functionalization of Transition Metal-bound Dinitrogen 29

1.5.5 Electrochemical and Photochemical Conversion of Dinitrogen Using Transition Metal Complexes 31

1.6 Catalytic Conversion of Dinitrogen into Ammonia Using Transition Metal Complexes 34

1.6.1 Catalytic Formation of Ammonia or Hydrazine Using Molybdenum Complexes 34

1.6.2 Catalytic Formation of Ammonia or Hydrazine Using Transition Metal Other than Molybdenum (Iron, Ruthenium, Osmium, Cobalt, and Vanadium) Complexes 40

1.6.3 Catalytic Transformation of Hydrazine into Ammonia 45

1.6.4 Catalytic Formation of Silylamine 47

1.7 Conclusion and Perspectives 50

References 51

2 Group 4 Transition MetalDinitrogen Complexes 79
*Hidetake Seino and Yuji Kajita*

2.1 Introduction 79

2.2 Preparation of Group 4 Transition MetalDinitrogen Complexes 80

2.2.1 Dinitrogen Complexes of Bis(cyclopentadienyl)titanium Derivatives 80

2.2.2 Dinitrogen Complexes of Bis(cyclopentadienyl)zirconium and Bis(cyclopentadienyl)hafnium Derivatives 89

2.2.3 Other Dinitrogen Complexes Based on Cyclopentadienyl Ligands 98

2.2.4 Dinitrogen Complexes Supported by -donor Ligands 100

2.2.5 Heterobimetallic Dinitrogen Complexes 109

2.3 Reactions of Group 4 Transition MetalDinitrogen Complexes 112

2.3.1 Protonation 112

2.3.2 Reduction 115

2.3.3 Reactions with Hydrogen 120

2.3.4 Reactions with SiH and BH Bonds 129

2.3.5 Reactions with Alkyl Halides and Their Equivalents 131

2.3.6 Reactions with Alkynes 136

2.3.7 Reactions with Carbon Dioxide and Cumulenes 138

2.3.8 Reactions with Carbon Monoxide 142

2.3.9 Dinitrogen Ligand Substitution 148

2.4 Conclusion and Perspectives 151

2.5 Addition After Acceptance of this Manuscript 151

References 152

3 Group 5 Transition Metal-Dinitrogen Complexes 159
*Leila M. Duman and Lawrence R. Sita*

3.1 Introduction 159

3.2 Preparation of Group 5 Metal N2 Complexes 160

3.2.1 Vanadium 160

3.2.2 Niobium 174

3.2.3 Tantalum 178

3.3 NN Bond CleavageWithin Group 5 Metal N2 Complexes 187

3.3.1 Vanadium 188

3.3.2 Niobium 192

3.3.3 Tantalum 197

3.4 Nitrogen Fixation Mediated by Group 5 Transition-metal N2 Complexes 201

3.4.1 Vanadium 202

3.4.2 Niobium 204

3.4.3 Tantalum 206

3.5 CPAM Group 5 Bimetallic (-1:1-N2) Complexes 206

3.6 Conclusions and Perspectives 212

References 214

4 Group 6 Transition MetalDinitrogen Complexes 221
*NicolasMézailles*

4.1 Introduction 221

4.2 Preparation of Group 6 Transition MetalDinitrogen Complexes 222

4.2.1 End-on Dinitrogen Complexes from N2 222

4.2.1.1 Arene and Phosphine Ligands 222

4.2.1.2 Thioether Ligands 226

4.2.1.3 Nitrogen and Cp Ligands 226 4.2.2 End-on Bridging Dinitrogen Complex...