Non-Noble Metal Catalysis Molecular Approaches and Reactions
, by Klein Gebbink, Robertus J. M.; Moret, Marc-Etienne
- ISBN: 9783527340613 | 3527340610
- Cover: Hardcover
- Copyright: 4/29/2019
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.
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.
Robertus Klein Gebbink, PhD, is full professor at Utrecht University, The Netherlands. His current research interests include homogeneous catalysis, organometallic chemistry, and bioinorganic chemistry, with a specific focus on iron-based catalysis, the immobilization of homogeneous catalysts and the catalytic conversion of biomass into chemical building blocks.
Marc-Etienne Moret, PhD, is assistant professor at Utrecht University, The Netherlands. His research interests lie in the organometallic chemistry of base metals with the aim of using these cheap, nontoxic metals to promote (in)organic transformations of environmental / industrial significance.
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
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