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非金属触媒:分子的アプローチと反応

Non-Noble Metal Catalysis : Molecular Approaches and Reactions

1

Klein Gebbink, Robertus J. M. (EDT)   Moret, Marc-Etienne (EDT)

Wiley-VCH 2018/12
616p.
出版国: DE
ISBN: 9783527340613
eISBN: 9783527699100
KNPID: EY00262880
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Full Description

An expert overview of current research, applications, and economic and environmental advantages

The study and development of new homogeneous catalysts based on first-row metals (Mn, Fe, Co, Ni, and Cu) has grown significantly due to the economic and environmental advantages that non-noble metals present. Base metals offer reduced cost, greater supply, and lower toxicity levels than noble metals?enabling greater opportunity for scientific investigation and increased development of practical applications. Non-Noble Metal Catalysis provides an authoritative survey of the field, from fundamental concepts and computational methods to industrial applications and reaction classes.

Recognized experts in organometallic chemistry and homogeneous catalysis, the authors present a comprehensive overview of the conceptual and practical aspects of non-noble metal catalysts. Examination of topics including non-innocent ligands, proton-coupled electron transfer, and multi-nuclear complexes provide essential background information, while areas such as kinetic lability and lifetimes of intermediates reflect current research and shifting trends in the field. This timely book demonstrates the efficacy of base metal catalysts in the pharmaceutical, fine-chemical, and agrochemical industries, addressing both environmental and economic concerns.

Providing essential conceptual and practical exploration, this valuable resource:

-Illustrates how unravelling new reactivity patterns can lead to new catalysts and new applications
-Highlights the multiple advantages of using non-noble metals in homogenous catalysis
-Demonstrates how the availability of non-noble metal catalysis reduces costs and leads to immense savings for the chemical industry
-Reveals how non-noble metal catalysis are more sustainable than noble metals such as palladium or platinum

Non-Noble Metal Catalysis: Molecular Approaches and Reactions is an indispensable source of up-to-date information for catalytic chemists, organic chemists, industrial chemists, organometallic chemists, and those seeking to broaden their knowledge of catalytic chemistry.

Table of Contents

Preface xvii

1 Application of Stimuli-Responsive and “Non-innocent” Ligands in BaseMetal Catalysis 1
Andrei Chirila, Braja Gopal Das, Petrus F. Kuijpers, Vivek Sinha, and Bas de Bruin

1.1 Introduction 1

1.2 Stimuli-Responsive Ligands 2

1.2.1 Redox-Responsive Ligands 3

1.2.2 pH-Responsive Ligands 5

1.2.3 Light-Responsive Ligands 7

1.3 Redox-Active Ligands as Electron Reservoirs 8

1.3.1 Bis(imino)pyridine (BIP) 8

1.3.1.1 Ethylene Polymerization with BIP 9

1.3.1.2 Cycloaddition Reactions 10

1.3.1.3 Hydrogenation and Hydro-addition Reactions 12

1.3.2 Other Ligands as Electron Reservoirs 14

1.4 Cooperative Ligands 15

1.4.1 Cooperative Reactivity with Ligand Radicals 16

1.4.1.1 Galactose Oxidase (GoAse) and its Models 16

1.4.1.2 Alcohol Oxidation by Salen Complexes 18

1.4.2 Base Metal Cooperative Catalysis with Ligands Acting as an Internal Base 18

1.4.2.1 Fe–Pincer Complexes 19

1.4.2.2 Ligands Containing a Pendant Base 20

1.5 Substrate Radicals in Catalysis 21

1.5.1 Carbene Radicals 22

1.5.2 Nitrene Radicals 25

1.6 Summary and Conclusions 26

References 27

2 Computational Insights into Chemical Reactivity and Road to Catalyst Design: The Paradigm of CO2 Hydrogenation 33
BhaskarMondal, Frank Neese, and Shengfa Ye

2.1 Introduction 33

2.1.1 Chemical Reactions: Conceptual Thoughts 33

2.1.2 Motivation behind Studying CO2 Hydrogenation 35

2.1.3 Challenges of CO2 Reduction 35

2.1.4 CO2 Hydrogenation 37

2.1.5 Noble vs Non-noble Metal Catalysis 38

2.1.6 CO2 Hydrogenation: Basic Mechanistic Considerations 38

2.2 Reaction Energetics and Governing Factor 39

2.3 Newly Designed Catalysts and Their Reactivity 42

2.4 Correlation between Hybridity and Reactivity 43

2.5 Concluding Remarks 45

Acknowledgments 46

References 47

3 Catalysis with Multinuclear Complexes 49
Neal P. Mankad

3.1 Introduction 49

3.2 Stoichiometric Reaction Pathways 50

3.2.1 Bimetallic Binding and Activation of Substrates 50

3.2.1.1 Small-Molecule Activation 51

3.2.1.2 Alkyne Activation 52

3.2.2 Bimetallic Analogs of Oxidative Addition and Reductive Elimination 53

3.2.2.1 E—H Addition and Elimination 54

3.2.2.2 C—X Activation and C—C Coupling 56

3.2.2.3 C=O Cleavage 57

3.3 Application in Catalysis 57

3.3.1 Catalysis with Reactive Metal–Metal Bonds 58

3.3.1.1 Bimetallic Alkyne Cycloadditions 58

3.3.1.2 Bimetallic Oxidative Addition/Reductive Elimination Cycling 59

3.3.2 Bifunctional and Tandem Catalysis without Metal–Metal Bonds 59

3.3.2.1 Cooperative Activation of Unsaturated Substrates 59

3.3.2.2 Cooperative Processes with Bimetallic Oxidative Addition and/or Reductive Elimination 62

3.4 Polynuclear Complexes 64

3.5 Outlook 65

Acknowledgments 66

References 66

4 Copper-Catalyzed Hydrogenations and Aerobic N—N Bond Formations: Academic Developments and Industrial Relevance 69
Paul L. Alsters and Laurent Lefort

4.1 Introduction 69

4.2 Cu-Promoted N—N Bond Formation 70

4.2.1 Noncyclization N—N or N=N Bond Formations 71

4.2.1.1 N—N Single-Bond-Forming Rea  ctions 71

4.2.1.2 N=N Double Bond-Forming Reactions 72

4.2.2 Cyclization N—N Bond Formations 74

4.2.2.1 Dehydrogenative Cyclizations 77

4.2.2.2 Eliminative Cyclizations 80

4.2.2.3 Eliminative Dehydrogenative Cyclizations 81

4.3 Cu-Catalyzed Homogeneous Hydrogenation 82

4.3.1 Hydrogenation of CO2 to Formate and Derivatives 84

4.3.2 Hydrogenation of Carbonyl Compounds 86

4.3.3 Hydrogenation of Olefins and Alkynes 89

4.4 Conclusions 91

References 92

5 C=C Hydrogenations with Iron Group Metal Catalysts 97
TimN. Gieshoff and Axel J. vonWangelin

5.1 Introduction 97

5.2 Iron 99

5.2.1 Introduction 99

5.2.2 Pincer Complexes 100

5.2.3 Others 106

5.3 Cobalt 107

5.3.1 Introduction 107

5.3.2 Pincer Complexes 108

5.3.3 Others 115

5.4 Nickel 118

5.4.1 Introduction 118

5.4.2 Pincer Complexes 119

5.4.3 Others 121

5.5 Conclusion 122

Acknowledgments 123

References 123

6 BaseMetal-Catalyzed Addition Reactions across C—C Multiple Bonds 127
Rodrigo Ramírez-Contreras and Bill Morandi

6.1 Introduction 127

6.2 Catalytic Addition to Alkenes Initiated Through Radical Mechanisms 128

6.2.1 Hydrogen Atom Transfer as a General Approach to Hydrofunctionalization of Unsaturated Bonds 128

6.2.2 Hydrazines and Azides via Hydrohydrazination and Hydroazidation of Olefins 128

6.2.2.1 Co- and Mn-Catalyzed Hydrohydrazination 128

6.2.2.2 Cobalt- and Manganese-Catalyzed Hydroazidation of Olefins 130

6.2.3 Co-Catalyzed Hydrocyanation of Olefins with Tosyl Cyanide 133

6.2.4 Co-Catalyzed Hydrochlorination of Olefins with Tosyl Chloride 133

6.2.5 FeIII/NaBH4-Mediated Additions of Unactivated Alkenes 134

6.2.6 Co-Catalyzed Markovnikov Hydroalkoxylation of Unactivated Olefins 135

6.2.7 Fe-Catalyzed Hydromethylation of Unactivated Olefins 137

6.2.8 Hydroamination of Olefins Using Nitroarenes to Obtain Anilines 137

6.2.9 Dual-Catalytic Markovnikov Hydroarylation of Alkenes 139

6.3 Other Catalytic Additions to Unsaturated Bonds Proceeding Through Initial R⋅ (R≠H) Attack 139

6.3.1 Cu-Catalyzed Trifluoromethylation of Unactivated Alkenes 139

6.3.2 Mn-Catalyzed Aerobic Oxidative Hydroxyazidation f Alkenes 139

6.3.3 Fe-Catalyzed Aminohydroxylation of Alkenes 141

6.4 Catalytic Addition to Alkenes Initiated Through Polar Mechanisms 143

6.4.1 Cu-Catalyzed Hydroamination of Alkenes and Alkynes 143

6.4.2 Ni-Catalyzed, Lewis-acid-Assisted Carbocyanation of Alkynes 147

6.4.3 Ni-Catalyzed Transfer Hydrocyanation 148

6.5 Hydrosilylation Reactions 150

6.5.1 Fe-Catalyzed, Anti-Markovnikov Hydrosilylation of Alkenes with Tertiary Silanes and Hydrosiloxanes 150

6.5.2 Highly Chemoselective Co-Catalyzed Hydrosilylation of Functionalized Alkenes Using Tertiary Silanes and Hydrosiloxanes 151

6.5.3 Alkene Hydrosilylation Using Tertiary Silanes with α-Diimine Ni Catalysts 151

6.5.4 Chemoselective Alkene Hydrosilylation Catalyzed by Ni Pincer Complexes 154

6.5.5 Fe- and Co-Catalyzed Regiodivergent Hydrosilylation of Alkenes 155

6.5.6 Co-Catalyzed Markovnikov Hydrosilylation of Terminal Alkynes and Hydroborylation of α-Vinylsilanes 155

6.5.7 Fe and Co Pivalate Isocyanide-Ligated Catalyst Systems for Hydrosilylation of Alkenes with Hydrosiloxanes 157

6.6 Conclusion 159

References 160

7 Iron-Catalyzed Cyclopropanation of Alkenes by Carbene Transfer Reactions 163
Daniela Intrieri, Daniela M. Carminati, and Emma Gallo

7.1 Introduction 163

7.2 Achiral Iron Porphyrin Catalysts 165

7.3 Chiral Iron Porphyrin Catalysts 172

7.4 Iron Phthalocyanines and Corroles 176

7.5 Iron Catalysts with N or N,O Ligands 180

7.6 The [Cp(CO)2FeII(THF)]BF4 Catalyst 184

7.7 Conclusions 186

References 187

8 Novel Substrates and Nucleophiles in Asymmetric Copper-Catalyzed Conjugate Addition Reactions 191
Ravindra P. Jumde, Syuzanna R. Harutyunyan, and Adriaan J.Minnaard

8.1 Introduction 191

8.2 Catalytic Asymmetric Conjugate Additions to α-Substituted α,β-Unsaturated Carbonyl Compounds 192

8.3 Catalytic Asymmetric Conjugate Additions to Alkenyl-heteroarenes 196

8.3.1 A Brief Overview of Asymmetric Nucleophilic Conjugate Additions to Alkenyl-heteroarenes 197

8.3.2 Copper-Catalyzed Asymmetric Nucleophilic Conjugate Additions to Alkenyl-heteroarenes 198

8.4 Conclusion 205

References 207

9 Asymmetric Reduction of Polar Double Bonds 209
Raphael Bigler, Lorena De Luca, Raffael Huber, and Antonio Mezzetti

9.1 Introduction 209

9.1.1 Catalytic Approaches for Polar Double Bond Reduction 209

9.1.2 The Role of Hydride Complexes 210

9.1.3 Ligand Choice and Catalyst Stability 211

9.2 Manganese 211

9.3 Iron 212

9.3.1 Iron Catalysts in Asymmetric Transfer Hydrogenation (ATH) 213

9.3.2 Iron Catalysts in Asymmetric Direct (H2) Hydrogenation (AH) 218

9.3.3 Iron Catalysts in Asymmetric Hydrosilylation (AHS) 220

9.4 Cobalt 223

9.4.1 Cobalt Catalysts in the AH of Ketones 223

9.4.2 Cobalt Catalysts in the ATH of Ketones 224

9.4.3 Cobalt Catalysts in Asymmetric Hydrosilylation 225

9.4.4 Asymmetric Borohydride Reduction and Hydroboration 226

9.5 Nickel 228

9.5.1 Nickel Catalysts in Asymmetric H2 Hydrogenation 228

9.5.2 Nickel ATH Catalysts 228

9.5.3 Nickel AHS Catalysts 229

9.5.4 Nickel-Catalyzed Asymmetric Borohydride Reduction 230

9.5.5 Ni-Catalyzed Asymmetric Hydroboration of α,β-Unsaturated Ketones 230

9.6 Copper 231

9.6.1 Copper-Catalyzed AH 231

9.6.2 Copper-Catalyzed ATH of α-Ketoesters 232

9.6.3 Copper-Catalyzed AHS of Ketones and Imines 232

9.7 Conclusion 235

References 235

10 Iron-, Cobalt-, and Manganese-Catalyzed Hydrosilylation of Carbonyl Compounds and Carbon Dioxide 241
Christophe Darcel, Jean-Baptiste Sortais, DuoWei, and Antoine Bruneau-Voisine

10.1 Introduction 241

10.2 Hydrosilylation of Aldehydes and Ketones 241

10.2.1 Iron-Catalyzed Hydrosilylation 242

10.2.2 Cobalt-Catalyzed Hydrosilylation 247

10.2.3 Manganese-Catalyzed Hydrosilylation 248

10.3 Reduction of Imines and Reductive Amination of Carbonyl Compounds 251

10.4 Reduction of Carboxylic Acid Derivatives 252

10.4.1 Carboxamides and Ureas 252

10.4.2 Carboxylic Esters 254

10.4.3 Carboxylic Acids 257

10.5 Hydroelementation of Carbon Dioxide 258

10.5.1 Hydrosilylation of Carbon Dioxide 258

10.5.2 Hydroboration of Carbon Dioxide 259

10.6 Conclusion 260

References 261

11 Reactive Intermediates and Mechanism in Iron-Catalyzed Cross-coupling 265
Jared L. Kneebone, Jeffrey D. Sears, andMichael L. Neidig

11.1 Introduction 265

11.2 Cross-coupling Catalyzed by Simple Iron Salts 266

11.2.1 Methods Overview 266

11.2.2 Mechanistic Investigations 267

11.3 TMEDA in Iron-Catalyzed Cross-coupling 273

11.3.1 Methods Overview 273

11.3.2 Mechanistic Investigations 275

11.4 NHCs in Iron-Catalyzed Cross-coupling 276

11.4.1 Methods Overview 276

11.4.2 Mechanistic Investigations 279

11.5 Phosphines in Iron-Catalyzed Cross-coupling 283

11.5.1 Methods Overview 283

11.5.2 Mechanistic Investigations 285

11.6 Future Outlook 291

Acknowledgments 291

References 291

12 Recent Advances in Cobalt-Catalyzed Cross-coupling Reactions 297
Oriol Planas, Christopher J.Whiteoak, and Xavi Ribas

12.1 Introduction 297

12.2 Cobalt-Catalyzed C—C CouplingsThrough a C—H Activation Approach 299

12.2.1 Low-Valent Cobalt Catalysis 299

12.2.2 High-Valent Cobalt Catalysis 302

12.3 Cobalt-Catalyzed C—C Couplings Using a Preactivated Substrate Approach (Aryl Halides and Pseudohalides) 308

12.3.1 Aryl or Alkenyl Halides, C(sp2)–X 308

12.3.2 Alkyl Halides, C(sp3)–X 309

12.3.3 Alkynyl Halides, C(sp)–X 311

12.3.4 Aryl Halides Without Organomagnesium 311

12.4 Cobalt-Catalyzed C—X Couplings Using C—H Activation Approaches 312

12.4.1 C—N Bond Formation 313

12.4.2 C—O and C—S Bond Formation 317

12.4.3 C—X Bond Formation (X=Cl, Br, I, and CN) 318

12.5 Cobalt-Catalyzed C—X Couplings Using a Preactivated Substrate Approach (Aryl Halides and Pseudohalides) 320

12.5.1 C(sp2)–S Coupling 320

12.5.2 C(sp2)–N Coupling 321

12.5.3 C(sp2)–O Coupling 322

12.6 Miscellaneous 322

12.7 Conclusions and Future Prospects 323

Acknowledgments 323

References 324

13 Trifluoromethylation and Related Reactions 329
Jérémy Jacquet, Louis Fensterbank, and Marine Desage-El Murr

13.1 Trifluoromethylation Reactions 329

13.1.1 Copper(I) Salts with Nucleophilic Trifluoromethyl Sources 329

13.1.1.1 Reactions with Electrophiles 330

13.1.1.2 Reactions with Nucleophiles: Oxidative Coupling 331

13.1.2 Generation of CF3 Radicals Using Langlois’ Reagent 332

13.1.3 Copper and Electrophilic CF3 + Sources 333

13.2 Trifluoromethylthiolation Reactions 341

13.2.1 Nucleophilic Trifluoromethylthiolation 342

13.2.1.1 Copper-Catalyzed Nucleophilic Trifluoromethylthiolation 342

13.2.1.2 Nickel-Catalyzed Nucleophilic Trifluoromethylthiolation 344

13.2.2 Electrophilic Trifluoromethylthiolation 345

13.3 Perfluoroalkylation Reactions 348

13.4 Conclusion 350

References 350

14 Catalytic Oxygenation of C=C and C—HBonds 355
Pradip Ghosh, Marc-Etienne Moret, and Robert J.M. Klein Gebbink

14.1 Introduction 355

14.2 Oxygenation of C=C Bonds 356

14.2.1 Manganese Catalysts 356

14.2.2 Iron Catalysts 363

14.2.3 Cobalt, Nickel, and Copper Catalysts 372

14.3 Oxygenation of C—H Bonds 376

14.3.1 Manganese Catalysts 376

14.3.2 Iron Catalysts 377

14.3.3 Cobalt Catalysts 380

14.3.4 Nickel Catalysts 381

14.3.5 Copper Catalysts 383

14.4 Conclusions and Outlook 384

Acknowledgment 385

References 385

15 Organometallic Chelation-Assisted C−H Functionalization 391
Parthasarathy Gandeepan and Lutz Ackermann

15.1 Introduction 391

15.2 C—C Bond Formation via C—H Activation 392

15.2.1 Reaction with Unsaturated Substrates 392

15.2.1.1 Addition to C—C Multiple Bonds 392

15.2.1.2 Addition to C—Heteroatom Multiple Bonds 393

15.2.1.3 Oxidative C—H Olefination 396

15.2.1.4 C—H Allylation 397

15.2.1.5 Oxidative C—H Functionalization and Annulations 397

15.2.1.6 C—H Alkynylations 403

15.2.2 C—H Cyanation 404

15.2.3 C—H Arylation 404

15.2.4 C—H Alkylation 407

15.3 C—Heteroatom Formation via C—H Activation 409

15.3.1 C—N Formation via C—H Activation 409

15.3.1.1 C—H Amination with Unactivated Amines 409

15.3.1.2 C—H Amination with Activated Amine Sources 409

15.3.2 C—O Formation via C—H Activation 412

15.3.3 C—Halogen Formation via C—H Activation 412

15.3.4 C—Chalcogen Formation via C—H Activation 414

15.4 Conclusions 415

Acknowledgments 415

References 415

16 CatalyticWater Oxidation:Water Oxidation to O2 Mediated by 3d Transition Metal Complexes 425
Zoel Codolá, Julio Lloret-Fillol, andMiquel Costas

16.1 Water Oxidation – From Insights into Fundamental Chemical Concepts to Future Solar Fuels 425

16.1.1 The Oxygen-Evolving Complex. A Well-Defined Tetramanganese Calcium Cluster 425

16.1.2 Synthetic Models for the Natural Water Oxidation Reaction 428

16.1.3 Oxidants in Water Oxidation Reactions 428

16.2 Model Well-Defined Water Oxidation Catalysts 430

16.2.1 Manganese Water Oxidation Catalysts 430

16.2.1.1 Bioinspired Mn4O4 Models 430

16.2.1.2 Biomimetic Models Including a Lewis Acid 432

16.2.1.3 Catalytic Water Oxidation with Manganese Coordination Complexes 433

16.2.2 Water Oxidation with Molecular Iron Catalysts 435

16.2.2.1 Iron Catalysts with Tetra-Anionic Tetra-Amido Macrocyclic Ligands 436

16.2.2.2 Mononuclear Complexes with Monoanionic Polyamine Ligands 437

16.2.2.3 Iron Catalysts with Neutral Ligands 437

16.2.2.4 Water Oxidation by a Multi-iron Catalyst 440

16.2.3 Cobalt Water Oxidation Catalysts 440

16.2.4 Nickel-Based Water Oxidation Catalysts 443

16.2.5 Copper-Based Water Oxidation Catalysts 445

16.3 Conclusion and Outlook 446

References 448

17 Base-Metal-Catalyzed Hydrogen Generation from Carbon- and Boron Nitrogen-Based Substrates 453
Elisabetta Alberico, Lydia K. Vogt, Nils Rockstroh, and Henrik Junge

17.1 Introduction 453

17.1.1 State of the Art of Hydrogen Generation from Carbon- and Boron Nitrogen-Based Substrates 453

17.1.2 Development of Base Metal Catalysts for Catalytic Hydrogen Generation 458

17.2 Hydrogen Generation from Formic Acid 460

17.2.1 Iron 461

17.2.2 Nickel 466

17.2.3 Aluminum 467

17.2.4 Miscellaneous 467

17.3 Hydrogen Generation from Alcohols 469

17.3.1 Hydrogen Generation with Respect to Energetic Application 469

17.3.2 Hydrogen Generation Coupled with the Synthesis of Organic Compounds 470

17.4 Hydrogen Storage in Liquid Organic Hydrogen Carriers 473

17.5 Dehydrogenation of Ammonia Borane and Amine Boranes 474

17.5.1 Overview on Conditions for H2 Liberation from Ammonia Borane and Amine Boranes 474

17.5.2 Non-noble Metal-Catalyzed Dehydrogenation of Ammonia Borane and Amine Boranes 476

17.6 Conclusion 480

References 481

18 Molecular Catalysts for Proton Reduction Based on Non-noble Metals 489
Catherine Elleouet, François Y. Pétillon, and Philippe Schollhammer

18.1 Introduction 489

18.2 Iron and Nickel Catalysts 489

18.2.1 Bioinspired Di-iron Molecules 490

18.2.2 Mono- and Poly-iron Complexes 496

18.2.3 Bioinspired [NiFe] Complexes and [NiMn] Analogs 501

18.2.4 Other Nickel-Based Catalysts 506

18.3 Other Non-noble Metal-Based Catalysts: Co, Mn, Cu, Mo, and W 508

18.3.1 Cobalt 508

18.3.2 Manganese 512

18.3.3 Copper 514

18.3.4 Group 6 Metals (Mo,W) 514

18.4 Conclusion 518

References 518

19 Nonreductive Reactions of CO2 Mediated by Cobalt Catalysts: Cyclic and Polycarbonates 529
Thomas A. Zevaco and ArjanW. Kleij

19.1 Introduction 529

19.2 Cocatalysts for CO2/Epoxide Couplings: Salen-Based Systems 530

19.3 Co–Porphyrins as Catalysts for Epoxide/CO2 Coupling 537

19.4 Cocatalysts Based on Other N4-Ligated and Related Systems 540

19.5 Aminophenoxide-Based Co Complexes 542

19.6 Conclusion and Outlook 544

Acknowledgments 545

References 545

20 Dinitrogen Reduction 549
Fenna F. van deWatering andzWojciech I. Dzik

20.1 Introduction 549

20.2 Activation of N2 550

20.3 Reduction of N2 to Ammonia 551

20.3.1 Haber–Bosch-Inspired Systems 551

20.3.2 Nitrogenase-Inspired Systems 555

20.3.2.1 Early Mechanistic Studies on N2 Reduction by Metal Complexes 556

20.3.2.2 Iron–Sulfur Systems 557

20.3.3 Catalytic Ammonia Formation 559

20.3.3.1 Tripodal Systems 560

20.3.3.2 Iron and Cobalt PNP Systems 566

20.3.3.3 The Cyclic Aminocarbene Iron System 567

20.3.3.4 The Diphosphine Iron System 568

20.4 Reduction of N2 to Silylamines 569

20.4.1 Iron 570

20.4.2 Cobalt 572

20.5 Conclusions and Outlook 575

Acknowledgments 576

References 576

Index 583