The field of transition metal catalysis has experienced incredible growth during the past decade. The reasons for this are obvious when one considers the world's energy problems and the need for new and less energy demanding syntheses of important chemicals. Heterogeneous catalysis has played a major industrial role; however, such reactions are generally not selective and are exceedingly difficult to study. Homogeneous catalysis suffers from on-site engineering difficulties; however, such reactions usually provide the desired selectivity. For example, Monsanto's synthesis of optically-active amino acids employs a chiral homogeneous rhodium diphosphine catalyst. Industrial uses of homogeneous catalyst systems are increasing. It is not by accident that many homogeneous catalysts contain tertiary phosphine ligands. These ligands possess the correct steric and electronic properties that are necessary for catalytic reactivity and selectivity. This point will be emphasized throughout the book. Thus the stage is set for a comprehensive be treatment of the many ways in which phosphine catalyst systems can designed, synthesized, and studied.

In the last decade there have been numerous advances in the area of rhodium-catalyzed hydroformylation, such as highly selective catalysts of industrial importance, new insights into mechanisms of the reaction, very selective asymmetric catalysts, in situ characterization and application to organic synthesis. The views on hydroformylation which still prevail in the current textbooks have become obsolete in several respects. Therefore, it was felt timely to collect these advances in a book. The book contains a series of chapters discussing several rhodium systems arranged according to ligand type, including asymmetric ligands, a chapter on applications in organic chemistry, a chapter on modern processes and separations, and a chapter on catalyst preparation and laboratory techniques. This book concentrates on highlights, rather than a concise review mentioning all articles in just one line. The book aims at an audience of advanced students, experts in the field, and scientists from related fields. The didactic approach also makes it useful as a guide for an advanced course.

An essential reference to the highly effective reactions applied to modern organic synthesis Rhodium complexes are one of the most important transition metals for organic synthesis due to their ability to catalyze a variety of useful transformations. Rhodium Catalysis in Organic Synthesis explores the most recent progress and new developments in the field of catalytic cyclization reactions using rhodium(I) complexes and catalytic carbon-hydrogen bond activation reactions using rhodium(II) and rhodium(III) complexes. Edited by a noted expert in the field with contributions from a panel of leading international scientists, Rhodium Catalysis in Organic Synthesis presents the essential information in one comprehensive volume. Designed to be an accessible resource, the book is arranged by different reaction types. All the chapters provide insight into each transformation and include information on the history, selectivity, scope, mechanism, and application. In addition, the chapters offer a summary and outlook of each transformation. This important resource: -Offers a comprehensive review of how rhodium complexes catalyze a variety of highly useful reactions for organic synthesis (e.g. coupling reactions, CH-bond functionalization, hydroformylation, cyclization reactions and others) -Includes information on the most recent developments that contain a range of new, efficient, elegant, reliable and useful reactions -Presents a volume edited by one of the international leading scientists working in the field today -Contains the information that can be applied by researchers in academia and also professionals in pharmaceutical, agrochemical and fine chemical companies Written for academics and synthetic chemists working with organometallics, Rhodium Catalysis in Organic Synthesis contains the most recent information available on the developments and applications in the field of catalytic cyclization reactions using rhodium complexes.

Ligand hybrid design is becoming an increasingly important area of the synthetic activity in organometallic chemistry. The coordination chemistry of diallylphosphines and phosphine-stabilized germylenes has been studied in this thesis. In particular, phosphine-stabilized germylenes have not only been studied by its potential use as ligands for transition metals, but also as possible synthetic tools in organic chemistry. Diallylphosphine behave as bidentate ligands to stabilize cationic rhodium species of type [Rh(COD){?3(P,C,C)RP(CH2CH=CH2)2}][BF4] [R= iPr2N, tBu and Ph]. Hemilabile properties of diallylphosphine ligands have been demonstrated by ligand exchange reactions. In solution, a dynamic equilibrium of exchange between the two allylic double bonds was detected by low temperature NMR analysis. In the same way, the reversible displacement of coordinated allylic double bond by acetonitrile could be observed. Theoretical calculations have been performed to explain the experimental results for the order of reactivity on removing the acetonitrile under vacuum. Germylenes stabilized by coordination of a phosphine ligand have been synthesized and fully characterized. Reactivity studies showed that phosphine-stabilized germylenes are unreactive toward unsaturated compounds, such as: alkyne, alkene and carbonyl derivatives, but reactive toward 2,3-dimethylbutadiene. The reactivity of phosphine-stabilized germylenes toward transition metal complexes have been studied by reaction with the dimer complex [Rh2(μ-Cl2)(COD)2], demonstrating that phosphine-stabilized germylenes are useful ligands with high potential in organometallic chemistry. The first isolable germanium analogue of alkynes, known as germyne, stabilized by coordination of a phosphine ligand has been synthesized and fully characterized. Synthesized germynes rearrange at RT affording a phosphaalkene and a new stable N-heterocyclic germylene. Keywords: Hybrid ligands, hemilabile properties, coordination chemistry, diallylphosphines, phosphine-stabilized germylene, germyne.