N-Heterocyclic Carbenes -- Contents -- Chapter 1 Introduction to N-Heterocyclic Carbenes: Synthesis and Stereoelectronic Parameters -- 1.1 Introduction -- 1.2 Electronic Structure and Stabilization of N-Heterocyclic Carbenes -- 1.3 N-Heterocyclic Carbene Ligands -- 1.3.1 Synthesis of NHC Precursors -- 1.3.2 Preparation of Free N-Heterocyclic Carbenes -- 1.4 Comparison of Different Types of N-Heterocyclic Carbenes -- 1.4.1 Carbenes Derived from Four-membered Heterocycles -- 1.4.2 Carbenes Derived from Five-membered Heterocycles -- 1.4.3 Heterocyclic Carbenes Containing Boron within the Heterocycle -- 1.4.4 N-Heterocyclic Carbenes Derived from Six- or Seven-membered Heterocycles -- 1.5 Conclusions and Outlook -- References -- Chapter 2 Computational Studies on the Reactivity of Transition Metal Complexes Featuring N-Heterocyclic Carbene Ligands -- 2.1 Introduction -- 2.2 Non-innocent Behaviour of NHCs at TM Centres -- 2.2.1 Reductive Elimination/Oxidative Addition -- 2.2.2 Migratory Insertion -- 2.2.3 Reactivity at the N-Substituents -- 2.3 Binding and Activation of Small Molecules at NHC-TM Complexes -- 2.4 Ru-catalysed Alkene Metathesis -- 2.5 Group 9 -- 2.6 Group 10 -- 2.7 Group 11 -- 2.8 Conclusions -- References -- Chapter 3 Synthesis, Activation and Decomposition of N-Heterocyclic Carbene-containing Complexes -- 3.1 Introduction -- 3.2 Synthetic Approaches to NHC-containing Metal Complexes -- 3.2.1 Early Investigations -- 3.2.2 Reaction with Isolated Carbenes -- 3.2.3 The Silver Oxide Method -- 3.2.4 Oxidative Addition -- 3.2.5 Generation of [(NHC)M] Complexes in Ionic Liquids -- 3.2.6 Reaction with C2-functionalized Carbene Adducts -- 3.2.7 Templated Synthesis of [(NHC)M] Complexes -- 3.3 Decomposition Reactions -- 3.3.1 C-H/C-C/C-N Bond Activation Reactions -- 3.3.2 Reductive Elimination.

3.3.3 Decomposition via Elimination of Protonated Carbene (Imidazolium Salt) -- 3.3.4 Migratory Insertion -- 3.3.5 Displacement Behavior -- 3.3.6 Miscellaneous Decomposition Reactions -- 3.4 Stability -- 3.4.1 Preventing Reductive Elimination -- 3.4.2 Inhibiting C-H Bond Activation -- 3.4.3 Preventing NHC Dissociation -- 3.5 Generation of the Active Species for NHC-containing Catalysts -- 3.5.1 NHC-containing Ruthenium Catalysts for Olefin Metathesis -- 3.5.2 Other Ruthenium-catalyzed Reactions Featuring NHCs -- 3.5.3 Palladium Catalysis -- 3.5.4 Nickel and Platinum NHC Catalysts -- 3.5.5 Activation by Extraction of Anionic Ligands -- 3.6 Conclusions -- References -- Chapter 4 Biologically Active N-Heterocyclic Carbene-Metal Complexes -- 4.1 Introduction -- 4.2 N-Heterocyclic Carbene-Silver Complexes -- 4.2.1 Medicinal Uses of Silver Complexes -- 4.2.2 Antimicrobial Properties of NHC-Silver(I) Complexes -- 4.2.3 Anti-tumour Activities of NHC-Silver(I) Complexes -- 4.3 N-Heterocyclic Carbene-Gold Complexes -- 4.3.1 Medicinal Uses of Gold -- 4.3.2 Antimicrobial Properties of NHC-Gold(I) Complexes -- 4.3.3 Anti-tumour Properties of NHC-Gold(I) and NHC-Gold(III) Complexes -- 4.4 Other Medically Relevant NHC-Metal Complexes -- 4.4.1 Antimicrobial Properties of NHC-Ruthenium(II) Complexes -- 4.4.2 Antimicrobial Properties of NHC-Rhodium(I) Complexes -- 4.4.3 Anti-tumour Activity of NHC-Palladium(II) Complexes -- 4.4.4 Anti-tumour Activity of NHC-Copper(I) Complexes -- 4.5 Conclusion -- References -- Chapter 5 Non-classical N-Heterocyclic Carbene Complexes -- 5.1 Introduction -- 5.2 Synthesis of Non-classical Carbene Complexes -- 5.3 Reactivity and Stability -- 5.4 Application in Catalysis -- 5.4.1 Cross-coupling Reactions -- 5.4.2 Hydrogenation and Hydrosilylation Reactions -- 5.4.3 Olefin Metathesis -- 5.4.4 Bond Activation -- 5.5 Conclusions.

References and Notes -- Chapter 6 Early Transition and Rare Earth Metal Complexes with N-Heterocyclic Carbenes -- 6.1 Introduction -- 6.2 Structural Survey and Typical Syntheses -- 6.2.1 Complexes with Monodentate NHC Ligands -- 6.2.2 Complexes with Anionic Multidentate NHC Ligands -- 6.2.3 Bimetallic Complexes with N-Heterocyclic Carbenes -- 6.3 Structure and Bonding -- 6.3.1 General Trends -- 6.3.2 Bonding -- 6.3.3 Distorted Geometries -- 6.4 Reactivity -- 6.5 Catalytic Applications -- 6.5.1 Polymerization of Ethene -- 6.5.2 Polymerization of Isoprene -- 6.5.3 Ring-opening Polymerizations -- 6.6 Conclusions and Outlook -- References -- Chapter 7 NHC-Iron, Ruthenium and Osmium Complexes in Catalysis -- 7.1 Introduction -- 7.2 NHC-Iron-catalysed Reactions -- 7.2.1 Organometallic and Electrochemical Reactions -- 7.2.2 Polymerisation Reactions -- 7.2.3 Cyclisation Reactions -- 7.2.4 C-C Bond Forming Reactions -- 7.3 NHC-Ruthenium-catalysed Reactions -- 7.3.1 Metathesis Reactions -- 7.3.2 Non-metathesis Reactions -- 7.3.3 Tandem Reactions -- 7.4 NHC-Osmium-catalysed Reactions -- 7.5 Conclusions and Outlook -- References -- Chapter 8 NHC-Cobalt, Rhodium and Iridium Complexes in Catalysis -- 8.1 Introduction -- 8.2 NHC-Cobalt Complexes -- 8.2.1 Stoichiometric Activation of Small Molecules -- 8.2.2 Cobalt-catalyzed Cyclizations -- 8.2.3 Activation of Carbon-Halogen Bonds -- 8.2.4 Miscellaneous Reactions -- 8.3 NHC-Rhodium Complexes -- 8.3.1 Arylation of Carbonyl and Related Compounds with Organoboron Reagents -- 8.3.2 Hydroformylations -- 8.3.3 Rhodium-catalyzed Cyclizations -- 8.3.4 Miscellaneous Reactions -- 8.4 NHC-Iridium Complexes -- 8.4.1 C-, N- and O-Alkylations -- 8.4.2 Hydroamination of Alkenes -- 8.4.3 Miscellaneous Reactions -- 8.5 Conclusions -- References -- Chapter 9 NHC-Palladium Complexes in Catalysis -- 9.1 Introduction.

9.2 C-C Bond Formation -- 9.2.1 Mizoroki-Heck Coupling and Related Chemistry -- 9.2.2 Suzuki-Miyaura Cross-coupling -- 9.2.3 Sonogashira Coupling -- 9.2.4 Application of the PEPPSI Protocol in Coupling Reactions -- 9.2.5 Immobilised Catalysts for Coupling Reactions -- 9.2.6 Pd-Allyl Mediated C-C Bond Formation -- 9.2.7 Direct Arylation by C-H Functionalisation -- 9.2.8 α-Carbonyl Arylation -- 9.2.9 Polymerisation Reactions -- 9.2.10 Telomerisation of Dienes -- 9.2.11 Miscellaneous C-C Bond-forming Reactions -- 9.3 C-N Bond Formation -- 9.3.1 Buchwald-Hartwig Aryl Amination -- 9.3.2 Allylic Amination -- 9.3.3 Miscellaneous C-N Bond-forming Reactions -- 9.4 Other transformations -- 9.5 Conclusions and Outlook -- References and Notes -- Chapter 10 NHC-Nickel and Platinum Complexes in Catalysis -- 10.1 Introduction -- 10.2 Preparation and Properties of NHC-Ni0 Complexes -- 10.3 Preparation and Properties of NHC-NiII Complexes -- 10.4 Dehalogenation and Dehydrogenation Mediated by NHC-Ni Complexes -- 10.4.1 Dehalogenation Mediated by NHC-Ni Complexes -- 10.4.2 Dehydrogenation Mediated by NHC-Ni Complexes -- 10.5 Activation/Cleavage of C-C, C-S or C-CN Bonds Mediated by NHC-Ni Complexes -- 10.6 Aryl Amination, Aryl Thiolation and Hydrothiolation Mediated by NHC-Ni Complexes -- 10.6.1 Aryl Amination Mediated by NHC-Ni Complexes -- 10.6.2 Arylthiolation Induced by NHC-Ni Complexes -- 10.6.3 Hydrothiolation of Alkynes Mediated by NHC-Ni Complexes -- 10.7 NHC-Ni-catalyzed Cross-coupling Reactions -- 10.7.1 NHC-Ni-catalyzed Corriu-Kumada Cross-couplings -- 10.7.2 NHC-Ni-catalyzed Organomanganese Cross-couplings -- 10.7.3 NHC-Ni-catalyzed Suzuki-Miyaura and Negishi Cross-couplings -- 10.8 Synthesis of Heterocyclic and Polycyclic Compounds by Cycloaddition Reactions -- 10.8.1 Pyrones from Diynes and Carbon Dioxide.

10.8.2 Pyridones or Pyrimidine-diones from Diynes or Alkynes and Isocyanates -- 10.8.3 Pyridines from Diynes and Nitriles -- 10.8.4 Pyrans from Unsaturated Hydrocarbons and Carbonyl Substrates -- 10.9 Cycloaddition of Alkynes to Unsaturated Derivatives -- 10.10 Ni-catalyzed Isomerization of Vinylcyclopropanes and Derivatives -- 10.11 Multi-component Reactions with Aldehydes and Ketones -- 10.12 Dimerization, Oligomerization and Polymerization Mediated by NHC-Ni Complexes -- 10.13 Syntheses of NHC-Pt Complexes -- 10.14 Cycloaddition Reactions Mediated by NHC-Pt Complexes -- 10.15 Cycloisomerization Reactions -- 10.16 Catalytic B-B and B-H Addition Reactions -- 10.17 Conclusion and Outlook -- References -- Chapter 11 NHC-Copper, Silver and Gold Complexes in Catalysis -- 11.1 Introduction -- 11.2 NHC-Cu in Catalysis -- 11.2.1 Conjugate Addition Reactions -- 11.2.2 Allylic Alkylation Reactions -- 11.2.3 Reduction Reactions -- 11.2.4 Boration Reactions -- 11.2.5 Cross-coupling Reactions -- 11.2.6 Miscellaneous Reactions -- 11.3 NHC-Ag in Catalysis -- 11.4 NHC-Au in Catalysis -- 11.4.1 Enyne Cycloisomerization and Related Reactions -- 11.4.2 Hydrofunctionalization of π-Bonds -- 11.4.3 Miscellaneous Reactions -- 11.5 Outlook -- References and Notes -- Chapter 12 Oxidation Reactions with NHC-Metal Complexes -- 12.1 Introduction -- 12.2 O2 Activation by NHC-Metal Complexes -- 12.3 Alcohol Oxidation -- 12.4 Alkene Oxidation -- 12.5 Alkane and Arene Oxidation -- 12.6 Conclusion -- References -- Chapter 13 Reduction Reactions with NHC-bearing Complexes -- 13.1 Introduction -- 13.2 Hydrogenation -- 13.2.1 Hydrogenation of Alkenes and Carbonyl Compounds -- 13.2.2 Asymmetric Catalysis -- 13.3 Transfer Hydrogenation -- 13.3.1 Carbonyl and Imine Reductions -- 13.3.2 Asymmetric Transfer Hydrogenation -- 13.3.3 Borrowing Hydrogen Methodology -- 13.4 Hydrosilylation.

13.4.1 Hydrosilylation of Alkenes.