Transition Metal Complexes of Neutral eta1-Carbon Ligands (Topics in Organometallic Chemistry Book 30)

Contents: Yves Canac and Remi Chauvin: Neutral eta1-carbon ligands: beyond carbon monoxide; Esteban P. Urriolabeitia: Ylide Ligands; Wolfgang Petz and Gernot Frenking: Carbodiphosphoranes and related ligands; Mareike C. Jahnke and F. Ekkehardt Hahn: Chemistry of N-Heterocyclic Carbene Ligands; Tsuyoshi Kato, Eddy Maerten, Antoine Baceiredo: Non-NHCs stable singlet carbene ligands; Victorio Cadierno, Sergio E. García-Garrido: All-Carbon-Substituted Allenylidene and Related Cumulenylidene Ligands; Victorio Cadierno, Sergio E. García-Garrido: Heteroatom-Conjugated Allenylidene and Related Cumulenylidene Ligands. Cover Page......Page 1 Topics in Organometallic Chemistry......Page 3 Title Page......Page 4 ISBN 978-3642047213......Page 5 Editors......Page 6 Topics in Organometallic Chemistry Also Available Electronically......Page 7 Preface......Page 8 Contents......Page 9 Neutral η1-Carbon Ligands: Beyond Carbon Monoxide......Page 10 The Underlying Ligand Typology: A Basic Lewis Analysis......Page 11 Class A. Neutral sp3-Carbon Ligands: Ylides and Carbodiphosphoranes......Page 15 Class B. Neutral sp2-Carbon Ligands: NHC and Non-NHC pi-Conjugated Carbenes......Page 17 Conclusion......Page 18 References......Page 19 Part I sp3 -Hybridized Neutral η1-Carbon Ligands......Page 22 Ylide Ligands......Page 24 Ylides: Basic Concepts......Page 25 Complexes with Ylides as Monodentate kappa1C Ligands......Page 29 Complexes with Ylides as Bidentate kappa1C-kappa1E Ligands......Page 39 Complexes with Ylides as Bidentate kappa2C,C Ligands......Page 43 References......Page 51 Carbodiphosphoranes and Related Ligands......Page 58 Introduction......Page 59 Theoretical Studies of Free Ligands CL2......Page 61 General Remarks......Page 65 Carbodiphosphoranes C(PR3)2......Page 69 Mixed Double Ylides CLL......Page 71 Carbon Suboxide......Page 72 Carbodicarbenes......Page 73 Cyclic Divalent C(0) Compounds (``Bent Allenes ́ ́)......Page 74 Theoretical Studies of Metal Complexes with Carbodiphosphoranes and Related Ligands......Page 75 Transition Metal Complexes of C(PPh3)2......Page 83 Transition Metal Complexes with C(PPh3)(CO) as eta1 Bonded Ligand......Page 91 Transition Metal Complexes with C(NHC)2 and with C{C(NMe2)2}2 as Ligands......Page 94 Transition Metal Complexes with Heterocyclic and Cyclic Divalent Carbon(0) Compounds as Ligands......Page 95 Summary and Outlook......Page 96 Additions in Proof......Page 97 References......Page 98 Part II sp2 -Hybridized Neutral η1-Carbon Ligands......Page 102 Chemistry of N-Heterocyclic Carbene Ligands......Page 104 Introduction......Page 105 N-Heterocyclic Carbene Ligands......Page 106 Preparation of the Free N-Heterocyclic Carbenes......Page 107 Comparison of Different N-Heterocyclic Carbenes......Page 109 Functionalized and Polydentate Carbene Ligands......Page 112 Common Routes to NHC Complexes......Page 113 Carbene Transfer Reactions......Page 114 Oxidative Addition vs Reductive Elimination Reactions......Page 115 Abnormal Carbenes......Page 120 Template Synthesis of NHC Complexes......Page 122 Additional Methods for the Preparation of NHC Complexes......Page 127 New Trends in the Chemistry of NHC Ligands......Page 129 References......Page 133 Non-NHCs Stable Singlet Carbene Ligands......Page 140 Push-Push System......Page 141 Push-Pull System......Page 142 Push-Spectator System......Page 143 Cyclopropenylidene Carbene......Page 145 Coordination Chemistry of Non-NHC Stable Carbenes......Page 146 Catalytic Reactions......Page 151 References......Page 154 Part III sp -Hybridized Neutral η1-Carbon Ligands......Page 158 All-Carbon-Substituted Allenylidene and Related Cumulenylidene Ligands......Page 160 Introduction......Page 161 Preparation of Allenylidene Complexes......Page 163 Group 4 Metals......Page 165 Group 7 Metals......Page 166 Iron......Page 168 Ruthenium......Page 169 Osmium......Page 174 Group 9 Metals......Page 176 Structure of Allenylidene Complexes......Page 177 Reactivity of Allenylidene Complexes......Page 182 Electrophilic Additions......Page 183 Group 6 Allenylidenes......Page 185 Group 7 Allenylidenes......Page 186 Group 8 Allenylidenes......Page 187 Group 9 Allenylidenes......Page 193 C-C Coupling Reactions......Page 194 Cycloaddition and Cyclization Reactions......Page 197 Catalytic Reactions Involving Allenylidene Complexes......Page 202 Olefin Metathesis......Page 203 Propargylic Substitution Reactions......Page 206 Other Catalytic Reactions......Page 210 Higher Cumulenylidene Complexes......Page 211 Preparation of Pentatetraenylidene Complexes......Page 212 Structure of Pentatetraenylidene Complexes......Page 214 Reactivity of Pentatetraenylidene Complexes......Page 215 Conclusions......Page 216 References......Page 217 Heteroatom-Conjugated Allenylidene and Related Cumulenylidene Ligands......Page 228 Introduction......Page 229 Group 6 Metals......Page 231 Group 8 Metals......Page 235 Structure of Allenylidene Complexes......Page 240 Group 6 Metals......Page 243 Group 8 Metals......Page 247 Pentatetraenylidene Complexes......Page 249 Heptahexaenylidene Complexes......Page 251 Complexes Containing Phosphonioacetylide Ligands......Page 252 Complexes Containing Tricarbon Monoxide......Page 256 References......Page 258 Index......Page 262 Cover Page 1 Topics in Organometallic Chemistry 3 Title Page 4 ISBN 978-3642047213 5 Editors 6 Topics in Organometallic Chemistry Also Available Electronically 7 Preface 8 Contents 9 Neutral η1-Carbon Ligands: Beyond Carbon Monoxide 10 Introduction 11 The Underlying Ligand Typology: A Basic Lewis Analysis 11 Descriptive Introduction of the Neutral spx-Carbon Ligands, x=3, 2, 1 15 Class A. Neutral sp3-Carbon Ligands: Ylides and Carbodiphosphoranes 15 Class B. Neutral sp2-Carbon Ligands: NHC and Non-NHC pi-Conjugated Carbenes 17 Class C. Neutral sp-Carbon Ligands: Amino- and Nonamino-Cumulenylidenes 18 Conclusion 18 References 19 Part I sp3 -Hybridized Neutral η1-Carbon Ligands 22 Ylide Ligands 24 Introduction 25 Ylides: Basic Concepts 25 Complexes with Ylides as Monodentate kappa1C Ligands 29 Complexes with Ylides as Bidentate kappa1C-kappa1E Ligands 39 Complexes with Ylides as Bidentate kappa2C,C Ligands 43 Summary 51 References 51 Carbodiphosphoranes and Related Ligands 58 Introduction 59 Theoretical Studies of Free Ligands CL2 61 Experimental Studies of Free Ligands CL2 65 General Remarks 65 Carbodiphosphoranes C(PR3)2 69 Mixed Double Ylides CLL 71 Cyclic Carbodiphosphoranes 72 Ketenylidenephosphoranes C(PR3)(CO) 72 Carbon Suboxide 72 Carbodicarbenes 73 Cyclic Divalent C(0) Compounds (``Bent Allenes ́ ́) 74 Theoretical Studies of Metal Complexes with Carbodiphosphoranes and Related Ligands 75 Experimental Studies of Metal Complexes with Carbodiphosphoranes and Related Ligands 83 Transition Metal Complexes of C(PPh3)2 83 Transition Metal Complex of the CLL Double Ylide C(PMeR2)(SPh2) 91 Transition Metal Complexes with Cyclic Carbodiphosphoranes 91 Transition Metal Complexes with C(PPh3)(CO) as eta1 Bonded Ligand 91 Transition Metal Complexes with C(NHC)2 and with C{C(NMe2)2}2 as Ligands 94 Transition Metal Complexes with Heterocyclic and Cyclic Divalent Carbon(0) Compounds as Ligands 95 Summary and Outlook 96 Additions in Proof 97 References 98 Part II sp2 -Hybridized Neutral η1-Carbon Ligands 102 Chemistry of N-Heterocyclic Carbene Ligands 104 Introduction 105 N-Heterocyclic Carbene Ligands 106 Synthesis of the Parent Azolium Salts and 2-Thiones 107 Preparation of the Free N-Heterocyclic Carbenes 107 Comparison of Different N-Heterocyclic Carbenes 109 Functionalized and Polydentate Carbene Ligands 112 Late Transition Metal Complexes with NHC Ligands 113 Common Routes to NHC Complexes 113 Carbene Transfer Reactions 114 Oxidative Addition vs Reductive Elimination Reactions 115 Remote Carbenes 120 Abnormal Carbenes 120 Template Synthesis of NHC Complexes 122 Additional Methods for the Preparation of NHC Complexes 127 New Trends in the Chemistry of NHC Ligands 129 References 133 Non-NHCs Stable Singlet Carbene Ligands 140 Introduction 141 Non-NHC Stable Carbenes and Their Properties 141 Push-Push System 141 Push-Pull System 142 Push-Spectator System 143 Cyclopropenylidene Carbene 145 Coordination Chemistry of Non-NHC Stable Carbenes 146 Catalytic Reactions 151 Conclusion 154 References 154 Part III sp -Hybridized Neutral η1-Carbon Ligands 158 All-Carbon-Substituted Allenylidene and Related Cumulenylidene Ligands 160 Introduction 161 Allenylidene Complexes 163 Preparation of Allenylidene Complexes 163 Group 4 Metals 165 Group 6 Metals 166 Group 7 Metals 166 Group 8 Metals 168 Iron 168 Ruthenium 169 Osmium 174 Group 9 Metals 176 Structure of Allenylidene Complexes 177 Reactivity of Allenylidene Complexes 182 Electrophilic Additions 183 Nucleophilic Additions 185 Group 6 Allenylidenes 185 Group 7 Allenylidenes 186 Group 8 Allenylidenes 187 Group 9 Allenylidenes 193 C-C Coupling Reactions 194 Cycloaddition and Cyclization Reactions 197 Catalytic Reactions Involving Allenylidene Complexes 202 Olefin Metathesis 203 Propargylic Substitution Reactions 206 Other Catalytic Reactions 210 Higher Cumulenylidene Complexes 211 Preparation of Pentatetraenylidene Complexes 212 Structure of Pentatetraenylidene Complexes 214 Reactivity of Pentatetraenylidene Complexes 215 Conclusions 216 References 217 Heteroatom-Conjugated Allenylidene and Related Cumulenylidene Ligands 228 Introduction 229 Allenylidene Complexes 231 Preparation of Allenylidene Complexes 231 Group 6 Metals 231 Group 8 Metals 235 Group 10 Metals 240 Structure of Allenylidene Complexes 240 Reactivity of Allenylidene Complexes 243 Group 6 Metals 243 Group 8 Metals 247 Higher Cumulenylidene Complexes 249 Pentatetraenylidene Complexes 249 Heptahexaenylidene Complexes 251 Complexes Containing Phosphonioacetylide Ligands 252 Complexes Containing Tricarbon Monoxide 256 Conclusions 258 References 258 Index 262 Neutral [eta]1-carbon ligands: Beyond carbon monoxide / Y. Canac, C. Lepetit and R. Chauvin Ylide ligands / E.P. Urriolabeitia Carbodiphosphoranes and related ligands / W. Petz and G. Frenking Chemistry of N-heterocyclic carbene ligands / M.C. Jahnke and F.E. Hahn Non-NHCs stable singlet carbene ligands / T. Kato, E. Maerten and A. Baceiredo All-carbon-substituted allenylidene and related cumulenylidene ligands / V. Cadierno and S. García-Garrido Heteroatom-conjugated allenylidene and related cumulenylidene ligands / V. Cadierno and S.E. García-Garrido. Contents: Yves Canac and Remi Chauvin: Neutral eta1-carbon ligands: beyond carbon monoxide; Wolfgang Petz and Gernot Frenking: Carbodiphosphoranes and related ligands; Tsuyoshi Kato, Eddy Maerten, Antoine Baceiredo: Non-NHCs stable singlet carbene ligands; Garcia-Garrido: All-Carbon-Substituted Allenylidene and Related Cumulenylidene Ligands;