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The bonding network and structural arrangement of simply borane polyhedra are initially discussed in this chapter. Borane clusters may be categorized as having closo, nido or arachno cages. A correlation between the total number of skeletal electrons, with the total number of skeletal atoms, was established by Wade in the form of a set of empirical rules. These were further extended to include the bonding in the heteroboranes, namely, [TeB10H11]- (5), [As2B9H10]- (6), [SB9H12]- (7) and [S2B6H9]- (8) which are of interest to the present work. Structure determination according to Wade's rules was further supported by results obtained from a symmetry Molecular Orbital (M.O.) theory approach. Numerous transition element derivatives of the heteroborane nido-[TeB10H11]- (5), nido-[As2B9H10]- (6), arachno-[SB9H12]- (7) and hypho-[S2B6H9]- (8) are reported in literature and have been characterized with each of the closo, nido, arachno and hypho structural classes. A general overview, with particular emphasizes on the structures of these metallaheteroboranes, has been given in this chapter. Phosphine ligands have played a major role in the chemistry of transition element complexes. The bidentate ligands dpm, dppe and dppf have been employed in the synthesis of monodentate, chelating and bridging metal complexes. Bis(diphenylphosphino)methane (dpm) can chelate to metals to form strained four-membered rings with small P-M-P angles. It also has a tendancy to act as a monodentate or bridging ligand. In contrast, bis(diphenylphosphino)ethane (dppe) is an excellent chelating ligand. Metal complexes containing the dppf ligand exhibit unusually large P-M-P angles. This thesis combines the chemistry of the heteroboranes nido-[TeB10H11]- (5), nido-[As2B9H10]- (6), arachno-[SB9H12]- (7) and hypho-[S2B6H9]- (8) with that of transition element complexes containing various bidentate ligands, to form neutral and cationic metallaheteroborane compounds. The influence of the ligands on the bonding and basic cage geometry of the metallaheteroboranes is discussed in detail. In addition the preferred mode of coordination of the dpm, and dppf lifands to the various heteroborane cages is also discussed.
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.
hemistry is the science about breaking and forming of bonds between atoms. One of the most important processes for organic chemistry is breaking bonds C–H, as well as C–C in various compounds, and primarily, in hydrocarbons. Among hydrocarbons, saturated hydrocarbons, alkanes (methane, ethane, propane, hexane etc. ), are especially attractive as substrates for chemical transformations. This is because, on the one hand, alkanes are the main constituents of oil and natural gas, and consequently are the principal feedstocks for chemical industry. On the other hand, these substances are known to be the less reactive organic compounds. Saturated hydrocarbons may be called the “noble gases of organic chemistry” and, if so, the first representative of their family – methane – may be compared with extremely inert helium. As in all comparisons, this parallel between noble gases and alkanes is not fully accurate. Indeed the transformations of alkanes, including methane, have been known for a long time. These reactions involve the interaction with molecular oxygen from air (burning – the main source of energy!), as well as some mutual interconversions of saturated and unsaturated hydrocarbons. However, all these transformations occur at elevated temperatures (higher than 300–500 °C) and are usually characterized by a lack of selectivity. The conversion of alkanes into carbon dioxide and water during burning is an extremely valuable process – but not from a chemist viewpoint.