Carbene

Presents the most innovative results in carbene chemistry, setting the foundation for new discoveries and applications The discovery of stable carbenes has reinvigorated carbene chemistry research, with investigators seeking to develop carbenes into new useful catalysts and ligands. Presenting the most innovative and promising areas of carbene research over the past decade, this book explores newly discovered structural, catalytic, and organometallic aspects of carbene chemistry, with an emphasis on new and emerging synthetic applications. Contemporary Carbene Chemistry features contributions from an international team of pioneering carbene chemistry researchers. Collectively, these authors have highlighted the most interesting and promising areas of investigation in the field. The book is divided into two parts: Part 1, Properties and Reactions of Carbenes, explores new findings on carbene stability, acid-base behavior, and catalysis. Carbenic structure and reactivity are examined in chapters dedicated to stable carbenes, carbodicarbenes, carbenes as guests in supramolecular hosts, tunneling in carbene and oxacarbene reactions, and ultrafast kinetics of carbenes and their excited state precursors. Theoretical concerns are addressed in chapters on computational methods and dynamics applied to carbene reactions. Part 2, Metal Carbenes, is dedicated to the synthetic dimensions of carbenes, particularly the reactions and catalytic properties of metal carbenes. The authors discuss lithium, rhodium, ruthenium, chromium, molybdenum, tungsten, cobalt, and gold. All the chapters conclude with a summary of the current situation, new challenges on the horizon, and promising new research directions. A list of key reviews and suggestions for further reading also accompanies every chapter. Each volume of the Wiley Series on Reactive Intermediates in Chemistry and Biology focuses on a specific reactive intermediate, offering a broad range of perspectives from leading experts that sets the stage for new applications and further discoveries.

The Organometallic Chemistry of N-heterocyclic Carbenes describes various aspects of N-heterocyclic Carbenes (NHCs) and their transition metal complexes at an entry level suitable for advanced undergraduate students and above. The book starts with a historical overview on the quest for carbenes and their complexes. Subsequently, unique properties, reactivities and nomenclature of the four classical NHCs derived from imidazoline, imidazole, benzimidazole and 1,2,4-triazole are elaborated. General and historically relevant synthetic aspects for NHCs, their precursors and complexes are then explained. The book continues with coverage on the preparation and characteristics of selected NHC complexes containing the most common metals in this area, i.e. Ni, Pd, Pt, Ag, Cu, Au, Ru, Rh and Ir. The book concludes with an overview and outlook on the development of various non-classical NHCs beyond the four classical types. Topics covered include: Stabilization, dimerization and decomposition of NHCs Stereoelectronic properties of NHCs and their evaluation Diversity of NHCs Isomers of NHC complexes and their identification NMR spectroscopic signatures of NHC complexes normal, abnormal and mesoionic NHCs The Organometallic Chemistry of N-heterocyclic Carbenes is an essential resource for all students and researchers interested in this increasingly important and popular field of research.

Highlights recent discoveries in the development of rapid kinetic techniques that allow for direct visualization and state-of-the-art computational methods.

With contributions by numerous experts

There are hardly more versatile compounds in organic synthesis than carbene complexes. The rapid development of new synthetic methods involving carbene complexes - stereoselective cyclopropanation, carbonyl olefination, olefin metathesis, etc. - reveals the value and high potential of these compounds. Their application ranges from the synthesis of fine chemicals to polymer production. This comprehensive, well structured handbook presents the fundamental principles and the recent advances in carbene complex chemistry. Arranged according to structure and reactivity, all relevant classes of carbene complexes, their generation, and application in organic synthesis are discussed in detail. Critically selected, up-to-date references and valuable experimental procedures await the reader. Every chemist searching for a concise introduction and reference work for carbene complex chemistry will welcome this practical guide. "...this concise presentation of all the aspects of the use of carbene complexes in synthesis will help provide the impetus for even more rapid developments in this field of research." R. H. Grubbs (Caltech)

In less than 20 years N-heterocyclic carbenes (NHCs) have become well-established ancillary ligands for the preparation of transition metal-based catalysts. This is mainly due to the fact that NHCs tend to bind strongly to metal centres, avoiding the need of excess ligand in catalytic reactions. Also, NHC‒metal complexes are often insensitive to air and moisture, and have proven remarkably resistant to oxidation. This book showcases the wide variety of applications of NHCs in different chemistry fields beyond being simple phosphine mimics. This second edition has been updated throughout, and now includes a new chapter on NHC‒main group element complexes. It covers the synthesis of NHC ligands and their corresponding metal complexes, as well as their bonding and stereoelectronic properties and applications in catalysis. This is complemented by related topics such as organocatalysis and biologically active complexes. Written for organic and inorganic chemists, this book is ideal for postgraduates, researchers and industrialists.

Summarizing the emerging field of N-heterocyclic carbenes used in organocatalysis, this is an excellent overview of the synthesis and applications of NHCs focusing on carbon-carbon and carbon-heteroatom bond formation. Alongside comprehensive coverage of the synthesis, characteristics and applications, this handbook and ready reference also includes chapters on NHCs for polymerization reactions and natural product synthesis.

In less than 20 years N-heterocyclic carbenes (NHCs) have become well-established ancillary ligands for the preparation of transition metal-based catalysts. This is mainly due to the fact that NHCs tend to bind strongly to metal centres, avoiding the need of excess ligand in catalytic reactions. Also, NHC‒metal complexes are often insensitive to air and moisture, and have proven remarkably resistant to oxidation. This book showcases the wide variety of applications of NHCs in different chemistry fields beyond being simple phosphine mimics. This second edition has been updated throughout, and now includes a new chapter on NHC‒main group element complexes. It covers the synthesis of NHC ligands and their corresponding metal complexes, as well as their bonding and stereoelectronic properties and applications in catalysis. This is complemented by related topics such as organocatalysis and biologically active complexes. Written for organic and inorganic chemists, this book is ideal for postgraduates, researchers and industrialists.

This book provides researchers in the fields of organic chemistry, organometallic chemistry and homogeneous catalysis with an overview of recent developments in the applications of reactions involving carbene and nitrene intermediates directed to the synthesis of heterocyclic compounds. Multiple pathways through which diverse heterocyclic compounds are accessed occur from a variety of carbene and nitrene precursors through C-H/X-H insertions, cycloadditions, ylide transformations, rearrangements, and cascade reactions. Catalytic processes that form metallo-carbenes and nitrenes offer unparalleled chemo-, regio-, and stereo-selectivities. Insights are provided into the scope of these methodologies and the inherent control of catalyst ligands on reaction selectivities.