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Recently, the synthesis of neutral and cationic group(VI) imido/oxo alkylidene N-heterocyclic carbene (NHC) complexes that tolerate protic functional groups and aldehydes was reported. Unprecedented turnover numbers of up to 1.2 million were found for their silica-supported representatives. Some group(VI) alkylidene NHC complexes even display stability towards moisture and air. Coordination of the NHC to tungsten imido bistriflate precursor complexes, however, can lead to undesired side reactions. This work consequently aimed at the development of novel, more efficient routes to neutral and cationic tungsten imido/oxo alkylidene NHC complexes. In addition, some molybdenum imido alkylidene NHC complexes were targeted. Thereby, the scope of synthetically accessible complexes was broadened and, subsequently, their reactivity in ring-opening metathesis polymerization (ROMP) was probed. Those complexes were used as thermally latent initiators for the ROMP of dicyclopentadiene. Precise determination of the onset temperature of polymerization was achieved via monitoring with differential scanning calorimetry. Furthermore, the selectivity of novel complexes was tested for the formation of stereoregular polymers through ROMP of enantiomerically pure norbornene derivatives, which allowed for the synthesis of up to 98% trans-isotactic or cis-syndiotactic polymers depending on the steric demand of the imido and the alkoxide ligand.
Surface organometallic chemistry is a new field bringing together researchers from organometallic, inorganic, and surface chemistry and catalysis. Topics ranging from reaction mechanisms to catalyst preparation are considered from a molecular basis, according to which the "active site" on a catalyst surface has a supra-molecular character. This. the first book on the subject, is the outcome of a NATO Workshop held in Le Rouret. France, in May. 1986. It is our hope that the following chapters and the concluding summary of recommendations for research may help to provide a definition of surface organometallic chemistry. Besides catalysis. the central theme of the Workshop, four main topics are considered: 1) Reactions of organometallics with surfaces of metal oxides, metals. and zeolites; 2) Molecular models of surfaces, metal oxides, and metals; 3) Molecular approaches to the mechanisms of surface reactions; 4) Synthesis and modification of zeolites and related microporous solids. Most surface organometallic chemistry has been carried out on amorphous high-surf ace-area metal oxides such as silica. alumina. magnesia, and titania. The first chapter. contributed by KNOZINGER. gives a short summary of the structure and reactivity of metal oxide surfaces. Most of our understanding of these surfaces is based on acid base and redox chemistry; this chemistry has developed from X-ray and spectroscopic data, and much has been inferred from the structures and reactivities of adsorbed organic probe molecules. There are major opportunities for extending this understanding by use of well-defined (single crystal) oxide surfaces and organometallic probe molecules.
Since the discovery of ferrocene and the sandwich-type complexes, the development of organometallic chemistry took its course like an avalanche and became one of the scientific success stories of the second half of the twentieth century. Based on this development, the traditional boundaries between inorganic and organic chemistry gradually disappeared and a rebirth of the nowadays highly important field of homogeneous catalysis occurred. It is fair to say that despite the fact that the key discovery, which sparked it all off, was made more than 50 years ago, organometallic chemistry remains a young and lively discipline.
The series Topics in Current Chemistry Collections presents critical reviews from the journal Topics in Current Chemistry organized in topical volumes. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience. Each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field.
Covering the complete breadth of the olefin metathesis reaction. The second edition of the ultimate reference in this field is completely updated and features more than 80% new content, with the focus on new developments in the field, especially in industrial applications. No other book covers the topic in such a comprehensive manner and in such high quality, and this new edition retains the three-volume format: Catalyst Development, Applications in Organic Synthesis and Polymer Synthesis. Edited by a Nobel laureate in the field, and with a list of contributors that reads like a "Who's-Who" of metathesis, this is an indispensable one-stop reference for organic, polymer and industrial chemists, as well as chemists working with organometallics. Individual volumes also available separately to purchase Volume 1: Catalyst Development - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527339485.html Volume 2: Applications in Organic Synthesis - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527339493.html Volume 3: Polymer Synthesis - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527339507.html
This book is a follow-up to Ivins Olefin Metathesis, (Academic Press, 1983). Bringing the standard text in the field up to date, this Second Edition is a result of rapid growth in the field, sparked by the discovery of numerous well-defined metal carbene complexes that can act as very efficient initiators of all types of olefin metathesis reaction, including ring-closing metathesis of acyclic dienes, enynes, and dienynes; ring-opening metathesis polymerizationof cycloalkenes, acyclic diene metathesis polymerization; and polymerization of alkynes, as well as simple olefin metathesis. Olefin Metathesis and Metathesis Polymerization provides a broad, up-to-date account of the subject from its beginnings in 1957 to the latest applications in organic synthesis. The book follows the same format as the original, making it useful toteachers and to researchers, and will be of particular interest to those working in the fields of organic chemistry, polymer chemistry, organometallic chemistry, catalysis, materials science and chemical engineering. - Discusses different classes of olefin metathesis and the choice of reaction conditions and catalyst - Considers commercial processes with examples from existing and new technologies - Provides a complete overview of the subject from its beginning to the present day
Organometallic chemistry is a well established research area at the interface of organic and inorganic chemistry. In recent years this field has undergone a ren aissance as our understanding of organometallic structure, properties and mechanism has opened the way for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as medicine, biology, materials and polymer sciences and organic synthesis. For example, in the de velopment of new catalytic processes, organometallic chemistry is helping meet the challenge to society that the economic and environmental necessities of the future pose. As this field becomes increasingly interdisciplinary, we recognize the need for critical overviews of new developments that are of broad significance. This is our goal in starting this new series Topics in Organometallic Chemistry. The scope of coverage includes a broad range of topics of pure and applied or ganometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. Topics in Organometallic Chemistry differs from existing review series in that each volume is thematic, giving an overview of an area that has reached a stage of maturity such that coverage in a single review article is no longer possible. Furthermore, the treatment addresses a broad audience of researchers, who are not specialists in the field, starting at the graduate student level. Discussion of possible future research directions in the areas covered by the individual volumes is welcome.
This first handbook to focus solely on the application of N-heterocyclic carbenes in synthesis covers metathesis, organocatalysis, oxidation and asymmetric reactions, along with experimental procedures. Written by leading international experts this is a valuable and practical source for every organic chemist.
In this book leading experts have surveyed major areas of application of NHC metal complexes in catalysis. The authors have placed a special focus on nickel- and palladium-catalyzed reactions, on applications in metathesis reactions, on oxidation reactions and on the use of chiral NHC-based catalysts. This compilation is rounded out by an introductory chapter and a chapter dealing with synthetic routes to NHC metal complexes.