N-Heterocyclic Carbenes

Steven P. Nolan was born in Canada. He received his B.Sc. in Chemistry from the University of West Florida and his Ph.D. from the University of Miami where he worked under the supervision of Professor Carl D. Hoff. After a postdoctoral stay with Professor Tobin J. Marks at Northwestern University, he joined the Department of Chemistry of the University of New Orleans in 1990. In 2006 he joined the Institute of Chemical Research of Catalonia (ICIQ) as Group leader and ICREA Research Professor. In early 2009, he joined the School of Chemistry at the University of St Andrews where he is Professor and holds the Chair in Inorganic chemistry.

Preface

N-HETEROCYCLIC CERBENES
Introduction
Structure and Properties of NHCs
Abnormal Carbenes
Why Are NHCs Stable?
Bonding of NHCs to Metal Centers
Quantifying the Properties of NHCs
N-Heterocyclic Carbenes in the Context of Other Stable Carbenes
Synthesis of NHCs
Salts and Adducts of NHCs
Summary

TUNING AND QUANTIFYING STERIC AND ELECTRONIC EFFECTS OF N-HETEROCYCLIC CARBENES
Introduction
Steric Effects in NHC ligands
Electronic Effects in NHC Ligands
Conclusions

CHIRAL MONODENDATE N-HETEROCYCLIC CARBENE LIGANDS IN ASYMMETRIC CATALYSIS
Introduction
NHC-Ru
NHC-Rh
NHC-Ir
NHC-Ni
NHC-Pd
NHC-Cu
NHC-Ag
NHC-Au
Conclusion

(N-HETEROCYCLIC CARBENE)-PALLADIUM COMPLEXES IN CATALYSIS
Introduction
Cross-Coupling Reactions
Chelates and Pincer Ligands
Asymmetric Catalysis
Oxidation Reactions
Telomerization, Oligomerization and Polymerization
Anticancer NHC-Pd Complexes

NHC PLATINUM(0) COMPLEXES: UNIQUE CATALYSTS FOR THE HYDROSILYLATION OF ALKENES AND ALKYNES
Introduction
Hydrosilylation of Alkenes: The Beginning
Initial Results with Phosphine Ligands
NHC Platinum(0) Complexes: The Breakthrough
Hydrosilylation of Alkynes
Conclusions

SYNTHESIS AND MEDICINAL PROPERTIES OF SILVER-NHC COMPLEXES AND IMIDAZOLIUM SALTS
Introduction
Silver-NHC Complexes as Antimicrobial Agents
Silver-NHC Complexes as Anticancer Agents
Conclusions

MEDICAL APPLICATIONS OF NHC-GOLD AND -COPPER COMPLEXES
Introduction
Gold Antimicrobial Agents
Metals as Antitumor Reagents
Copper Complexes as Antitumoral Reagents
Conclusion

NHC-COPPER COMPLEXES AND THEIR APPLICATIONS
Introduction
History of NHC-Copper Systems
Hydrosilylation
Allene Formation
1,4-Reduction
Conjugate Addition
Hydrothiolation, Hydroalkoxylation, Hydroamination
Carboxylation and Carbonylation (via Boronic Acids, CH Activation): CO2 Insertion
[3 + 2] Cycloaddition Reaction: Formation of Triazole
Allylic Substitution
Carbene and Nitrene Transfer
Boration Reaction
Olefination of Carbonyl Derivatives
Copper-Mediated Cross-Coupling Reaction
Fluoride Chemistry
Other Reactions
Transmetalation
Conclusion

NHC-AU(I) COMPLEXES: SYNTHESIS, ACTIVATION, AND APPLICATION
Introduction
Synthesis of NHC-Gold(I) Chlorides
Activation of NHC-Au(I) Chlorides
Applications of NHC-Au(I) Catalysts
Conclusion

RECENT DEVELOPMENTS IN THE SYNTHESIS AND APPLICATIONS OF RHODIUM AND IRIDIUM COMPLEXES BEARING N-HETEROCYCLIC CARBENE LIGANDS
Introduction
Rh- and Ir-NHC-Based Complexes: Structural and Electronic Features Mono-NHCs
Catalytic Applications of Rhodium and Iridium NHC-Based Complexes
Abbreviations

N-HETEROCYCLIC CARBENE?RUTHNIUM COMPLEXES: A PROMINENT BREAKTHROUGH IN METATHESIS REACTIONS
Introduction
Variations of NHC in Ruthenium Complexes
Modifications in Imidazol- and Imidazolin-2-ylidene Ligands
Influence of Symmetrically 1,3-Substituted N-Heterocyclic Carbene in Metathesis
Unsymmetrically N,N'-Substituted N-Heterocyclic Carbenes

RUTHENIUM N-HETEROCYCLIC CARBENE COMPLEXES FOR THE CATALYSIS OF NONMETATHESIS ORGANIC TRANSFORMATIONS
Introduction
Transfer Hydrogenation
Direct Hydrogenation (and Hydrosilylation)
Borrowing Hydrogen
Alcohol Racemization
Arylation
Reactions of Alkynes
Isomerization of C=C Bonds
Allylic Substitution Reactions
Miscellaneous Reactions
Conclusions

NICKEL COMPLEXES OF N-HETEROCYCLIC CARBENES
Introduction
Nickel-NHC Catalysts
Cross-Coupling Reactions
Oxidation/Reduction Reactions
Hydrosilylation
Cycloadditions
Isomerization
Reductive Coupling
Conclusions and Outlook

COODINATION CHEMISTRY, RACTIVITY, AND APPLICATIONS OF EARLY TRANSITION METAL COMPLEXES BEARING N-HETEROCYCLIC CARBENE LIGANDS
Introduction
Group 3 Metal Complexes
Group 4 Metal Complexes
Group 5 Metal Complexes
Group 6 Metal Complexes
Group 7 Metal Complexes
Conclusion

NHC COMPLEXES OF MAIN GROUP ELEMNTES: NOVEL STRUCTURES, REACTIVITY, AND CATALYTIC BEHAVIOR
Introduction
Structures of Common NHCs for Main Group Chemistry
NHC Complexes of Group 1 Elements
NHC Complexes of Group 2 Elements
NHC Complexes of Group 13 Elements
NHC Complexes of Group 14 Elements
NHC Complexes of Group 15 Elements
NHC Complexes of Group 16 Elements
NHC Complexes of Group 17 Elements
NHC Reactivity with Protic Reagents
Cyclic Alkyl Amino Carbenes: Closely Related Cyclic Cousins to NHCs with Similar and Differing Reactivities
Summary and Outlook

CATALYSIS WITH ACYCLIC AMINOCARBENE LIGANDS: ALTERNATIVES TO NHCs WITH DISTINCT STERIC AND ELCTRONIC PROPERTIES
Introduction
Metalation Routes of Acyclic Carbene Ligands
Ligand Properties of Acyclic Carbenes
Catalytic Applications
Frontiers in Acyclic Carbene Chemistry
Conclusion

Index