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Non-Noble Metal Catalysis

Molecular Approaches and Reactions
1. Aufl.

von: Robertus J. M. Klein Gebbink, Marc-Etienne Moret
160,99 €
Verlag:	Wiley-VCH
Format:	PDF
Veröffentl.:	19.12.2018
ISBN/EAN:	9783527699117
Sprache:	englisch
Anzahl Seiten:	616

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Titelbeschreibung

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.

Inhaltsverzeichnis

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

Autorenportrait

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.

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An expert overview of current research and applications 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, computational modeling, 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 highlights the efficacy of base metal catalysts for numerous chemical transformations applied in the pharmaceutical, fine chemical, and agrochemical industries, providing opportunities for more economical and environmentally benign processes. Providing essential conceptual and practical exploration, this valuable resource: <ul> <li>Illustrates how unravelling new reactivity patterns can lead to new catalysts and new applications</li> <li>Highlights the multiple advantages of using non-noble metals in homogenous catalysis</li> <li>Provides an overview of recent developments in many industrially relevant transformations</li> <li>Demonstrates that non-noble metals can offer competitive, sustainable alternatives to noble metals in homogeneous catalysis</li> </ul> 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.