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The bite angle of a diphosphine ligand plays an important role in determining the reactivity of a transition metal complex. The coordinated dihydrogen on a transition metal center can be activated toward homolysis or heterolysis depending upon the nature of the metal center and the ancillary ligand environment. The present work deals with our investigations on the effect of the bite angle of the chelating diphosphine ligands in the chemistry of certain ruthenium hydride and dihydrogen complexes. Protonation of the ds-[Ru(H)2(dppm)(PPh3)2] (dppm = Ph2PCH2PPh2) using HBF4-Et2O resulted in the dihydrogen/hydride complex trans-(Formula). This species shows dynamic exchange of the H-atom between the dihydrogen and the hydride ligands. The H-atom site exchange was studied by NMR spectroscopy. Attempts to prepare the ruthenium dihydride complexes, cis-[Ru(H)2(dppe)(PPh3)2] (dppe = Ph2PCH2CH2PPh2) and cw-[Ru(H)2(dppp)(PPh3)2] (dppp = Ph2PCH2CH2CH2PPh2) with larger bite-angled diphosphines dppe and dppp were unsuccessful. Earlier work in our group on the effect of trans nitrile ligands in a series of complexes of the type (Formula)howed that the properties of the bound H2 are almost invariant with a change in the R group of the nitrile. hi an effort to compare those results with analogous ruthenium complexes bearing smaller bite-angled diphosphine, dppm, we synthesized and characterized a series of complexes of the type (Formula). We found that the properties of the bound H2 were once again invariant with a change in the R group of the nitrile. In an effort to compare the effect of having two diphosphine ligands of different bite angles with systems containing symmetrical diphosphine ligands reported by our group,3 we synthesized a series of complexes of the type (Formula). These complexes exhibit hybrid properties in comparison to systems with symmetrical diphosphine ligands in terms of spectroscopic features and chemical reactivity. Thus, the bite angle of the diphosphine.
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.
Research on dendrimers has exploded in the last 15 years, moving from the establishment of synthetic methodologies, particularly in the early years up to the end of nineties, towards sophisticated and wide-ranging applications. Dendrimers play an important role in many different areas, spanning from basic synthetic approaches to artificial photosynthesis, to medicine, to catalysis. The great potential of dendrimers is well-recognized by the hundreds of papers in the field and the increasing number of patents, and stimulated developments in other areas of knowledge, including new characterization techniques. However, some basic principles and methods still continue to give a unity to the field. Although several books on dendrimers have been published during these 15 years, the very recent progresses in new areas now requires a new point of view, trying to give a unifying and comprehensive outlook of the field. Since the first dendrimer was synthesized by Vögtle in 1978, dendrimers have experienced an explosion of scientific interest because of their unique molecular architecture. This resulted in over 5,000 scientific papers and patents published by the end of 2005. The proposed book will cover both fundamental and applicative aspects of dendrimer research. Chapters devoted to basic principles, synthetic methods and strategies, and advanced characterization techniques will be integrated by chapters illustrating the full potential of dendrimers in various fields, like artificial photosynthesis, multi-redox pool systems, diagnostics, biomedical and sensing purposes, design of functional nanostructures. Particular emphasis will be devoted to possible future developments.
Based on Collman et al.'s best-selling classic book, Principles and Applications of Organotransition Metal Chemistry, Hartwig's text consists of new or thoroughly updated and restructured chapters and provides an in-depth view into mechanism, reaction scope, and applications. It covers the most important developments in the field over the last twenty years with great clarity with a selective, but thorough and authoritative coverage of the fundamentals of organometallic chemistry, the elementary reactions of these complexes, and many catalytic processes occurring through organometallic intermediates, making this the Organotransition Metal Chemistry text for a new generation of scientists.
Among the various nanomaterials, inorganic nanoparticles are extremely important in modern technologies. They can be easily and cheaply synthesized and mass produced, and for this reason, they can also be more readily integrated into applications. Inorganic Nanoparticles: Synthesis, Applications, and Perspectives presents an overview of these special materials and explores the myriad ways in which they are used. It addresses a wide range of topics, including: Application of nanoparticles in magnetic storage media Use of metal and oxide nanoparticles to improve performance of oxide thin films as conducting media in commercial gas and vapor sensors Advances in semiconductors for light-emitting devices and other areas related to the energy sector, such as solar energy and energy storage devices (fuel cells, rechargeable batteries, etc.) The expanding role of nanosized particles in the field of catalysis, art conservation, and biomedicine The book’s contributors address the growing global interest in the application of inorganic nanoparticles in various technological sectors. Discussing advances in materials, device fabrication, and large-scale production—all of which are urgently required to reduce global energy demands—they cover innovations in areas such as solid-state lighting, detailing how it still offers higher efficiency but higher costs, compared to conventional lighting. They also address the impact of nanotechnology in the biomedical field, focusing on topics such as quantum dots for bioimaging, nanoparticle-based cancer therapy, drug delivery, antibacterial agents, and more. Fills the informational gap on the wide range of applications for inorganic nanoparticles in areas including biomedicine, electronics, storage media, conservation of cultural heritage, optics, textiles, and cosmetics Assembling work from an array of experts at the top of their respective fields, this book delivers a useful analysis of the vast scope of existing and potential applications for inorganic nanoparticles. Versatile as either a professional research resource or textbook, this effective tool elucidates fundamentals and current advances associated with design, characterization, and application development of this promising and ever-evolving device.
R. Haag, S. Roller: Polymeric Supports for the Immobilisation of Catalysts .- J. Horn, F. Michalek, C.C. Tzschucke, W. Bannwarth: Non-Covalently Solid-Phase Bound Catalysts for Organic Synthesis .- Y. Uozumi: Recent Progress in Polymeric Palladium Catalysts for Organic Synthesis .- D.E. Bergbreiter, J. Li: Applications of Catalysts on Soluble Supports .- B. Desai, C.O. Kappe: Microwave-Assisted Synthesis Involving Immobilized Catalysts .- A. Kirschning, G. Jas: Applications of Immobilized Catalysts in Continuous Flow Processes .- N. End, K.-U. Schöning: Immobilized Catalysts in Industrial Research and Application .- N. End, K.-U. Schöning: Immobilized Biocatalysts in Industrial Research and Production
The Inorganic Syntheses series provides inorganic chemists with detailed and foolproof procedures for the preparation of important and timely compounds. Volume 33 includes provocative contributions on syntheses of selected supramolecules, useful reagents/ligands, solid state materials/clusters, and other compounds of general interest.
This volume of Inorganic Syntheses spans the preparations of wide range of important inorganic, organometallic and solid-state compounds. The volume is divided into 6 chapters. The first chapter contains the syntheses of some key early transition metal halide clusters and the very useful mononuclear molybdenum(III) synthon, MoCl3(THF)3. Chapter 2 covers the synthesis of a number of cyclopentadienyl compounds, including a novel route to sodium and potassium cyclopentadienide, MC5H5. Chapter 3 details synthetic procedures for a range of metal-metal bonded compounds, including several with metal-metal multiple bonds. Chapter 4 contains procedures for a range of early and late transition metal compounds, each a useful synthon for further synthetic elaboration. Chapter 5 deals with the synthesis of a number of main group compounds and ligands, while Chapter 6 covers teaching laboratory experiments.