Carbene

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

Carbenes are important molecules in chemistry because of their photochemistry and high reactivity. They have many potential applications in medicinal and materials chemistry. This book provides a comprehensive introduction to carbenes and discusses their characteristics, structure, and synthesis procedures. It gives special emphasis to N-heterocyclic carbenes (NHCs) and their metal complexes.

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.

Our understanding of carbene chemistry has advanced dramatically, especially in the last decade, and new developments continue to emerge. Some of the recent exciting findings have been collected in the first and second volumes of Advances in Carbene Chemistry. With the third volume, the series continues to provide a periodic coverage of carbene chemistry in its broadest sense. Beginning as chemical curiosities, carbenes are now solidly established as reactive intermediates with fascinating and productive research areas of their own. Five decades of divalent carbon chemistry have provided us with a vast repertoire of new, unusual, and surprising reactions. Some of those reactions, once classified as exotic, have become standard methods in organic synthesis. These highly reactive carbene species have been harnessed and put to work to achieve difficult synthetic tasks other reactive intermediates cannot easily perform. The fruitful relationship between experiment and theory has pushed carbene chemistry further toward the direction of reaction control; that is, regio- and stereoselectivity in intra- and intermolecular addition and insertion reactions. The interplay between experiment and modern spectroscopy has led to the characterization of many carbenes that are crucial to both an understanding and further development of this field.

Organic Chemistry, Volume 1: Carbene Chemistry is a 12-chapter text that covers pertinent research studies on the carbene chemistry. The first ten chapters are devoted to comprehensive surveys of carbene chemistry. Each chapter tackles specific carbene compound, such as olefinic and acetylenic carbenes, aryl and diarylcarbenes, carboalkoxycarbenes, ketocarbenes, halocarbenes, heteroatom-containing carbenes, and dicarbenes. The formation, synthesis, and reactions of these compounds are discussed. The remaining two chapters the excess energy in reactions and spin states of carbenes. This book will be of value to organic chemists, organic chemistry researchers, teachers, and students.

Over the last fifteen years, N-heterocyclic carbenes (NHCs) have mostly been used as ancillary ligands for the preparation of transition metal-based catalysts. Compared to phosphorus-containing ligands, NHCs tend to bind more strongly to metal centres, avoiding the necessity for the use of excess ligand in catalytic reactions. The corresponding complexes are often less sensitive to air and moisture, and have proven remarkably resistant to oxidation. Recent developments in catalysis applications have been facilitated by the availability of carbenes stable enough to be bottled, particularly for their use as organocatalysts. This book shows how N-heterocyclic carbenes can be useful in various fields of chemistry and not merely laboratory curiosities or simple phosphine mimics. NHCs are best known for their contribution to ruthenium and palladium-catalysed reactions but the scope of this book is much broader. The synthesis of NHC ligands and their corresponding metal complexes are covered in depth. Moreover, the biological activity of NHC-containing complexes, as well as an overview of their theoretical aspects are included. Such metal species are further examined, not only in terms of their catalytic applications, but also of their stereoelectronic parameters and reactivity/stability. Finally, special attention is given to the hot topic of organocatalysis. The book will be of interest to postgraduates, academic researchers and those working in industry.

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)