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Two new bidentate thioether ligands, the dialkylbis[(alkylthio)methyl]silanes Ph[subscript]2Si(CH[subscript]2SMe)[subscript]2 and Me[subscript]2Si(CH[subscript]2SBu[superscript]t)[subscript]2, have been synthesized and fully characterized. Reactivity studies led to the isolation of group 11 and 12 metal halide complexes, all of which have d[superscript]10 electronic configurations. The full characterization of these complexes, including NMR spectroscopy and elemental analysis, will be described in this thesis. Reactivity studies of R'[subscript]2Si(CH[subscript]2SR)[subscript]2 (R' = Ph, Me; R = Me, Bu[superscript]t) towards monovalent coinage metal ions have produced simple 1:1 and 1:2 complexes {R'[subscript]2Si(CH[subscript]2SR)[subscript]2}CuX (X = C1, Br, I), {R'[subscript]2Si(CH[subscript]2SR)[subscript]2}AgX (X = NO[subscript]3, OTf) and [Ag{R'[subscript]2Si(CH[subscript]2SR)[subscript]2}[subscript]2]X (X = BF[subscript]4, SbF[subscript]). With Ph[subscript]2Si(CH[subscript]2SMe)[subscript]2, the majority of these 1:1 complexes showed dimeric structures, similar in most cases to the Me[subscript]2Si(CH[subscript]2SMe)[subscript]2 analogues. It was concluded that changing substituents on silicon did not affect considerably the geometry of the complexes. However, the bulky substituents on the thioether Me[subscript]2Si(CH[subscript]2SBu[superscript]t)[subscript]2 preclude the generation of polymeric (or dimeric) species such as those isolated for R = Me and result instead in the formation of rare examples of three-coordinate trigonal planar Cu(I) thioether complexes. Furthermore, these are some of the first complexes exhibiting [CuS[subscript]2X] coordination spheres. In a similar vein, the dinuclear gold complexes Au[subscript]2{Me[subscript]2Si(CH[subscript]2SBu[superscript]t)[subscript]2}X[subscript]2 (X = C1, Br), each of which displays a weak intramolecular Au...Au aurophilic interaction and photoluminescent properties, are obtained instead of the polymeric species isolated for closely related but less sterically demanding thioether ligands [e.g., Me[subscript]2Si(CH[subscript]2SMe)[subscript]2]. The new complexes have been characterized by a variety of analytical and spectroscopic techniques, including electrospray ionization mass spectrometry (ESIMS). An overview of the coordination chemistry of R'[subscript]2Si(CH[subscript]2SR)[subscript]2 towards other transition metal ions such as Cd(II) and Hg(II) will be also discussed.
ABSTRACT: The new thioethers MeSi and Si have been synthesized with the goal of investigating the effect of the tert-butyl substituents on their structure and coordination chemistry. These tridentate or tetradentate ligands are new members of existing families of acyclic thioethers. Reactivity studies of these newly synthesized ligands were performed by coordinating them to group 6 metal carbonyl derivatives. These complexes have been compared with the group 6 metal complexes of other thioether ligands to determine the electronic and steric differences that the tert-butyl group may cause. Spectroscopic and X-ray diffraction studies were performed to determine those effects.
ABSTRACT: The new acyclic tetradentate thioether ligand tetrakis[(methylthio)methyl]silane, has been synthesized with the goal of studying its coordination chemistry and comparing it with that of the recently prepared methyltris[(methylthio)methyl]silane, and other tridentate or tetradentate thioethers. This new tetradentate ligand was coordinated to the group 6 transition metals to give a complete series of thioether carbonyl complexes, where the sulfur ligand is bound to the metal center in either a bidentate or tridentate fashion. The dinuclear compounds were obtained from the reaction of LM(CO)4 and [Cu(NCMe)4]X (X = BF4 or PF6) in a 2:1 ratio, with the thioether serving as a bridging ligand between the two metals. Furthermore, six and seven-coordinated dihalo thioether complexes have also been prepared and structurally characterized.
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With an enormous velocity, olefin polymerization has expanded to one of the most significant fields in polymers since the first industrial use about 50 years ago. In 2005, 100 million tons of polyolefins were produced - the biggest part was catalyzed by metallorganic compounds. The Hamburg Macromolecular Symposium 2005 with the title "Olefin Polymerization" involved topics such as new catalysts and cocatalysts, kinetics, mechanism and polymer reaction engineering, synthesis of special polymers, and characterization of polyolefins. The conference combined scientists from different disciplines to discuss latest research results of polymers and to offer each other the possibility of cooperation. This is reflected in this volume, which contains invited lectures and selected posters presented at the symposium.
The Progress in Inorganic Chemistry series provides inorganic chemistry with a forum for critical, authoritative evaluations of advances in every area of the discipline. Volume 52, Dithiolene Chemistry: Synthesis, Properties, and Applications continues this forum with a focus on dithiolene chemistry and a significant, up-to-date selection of papers by internationally recognized researchers. Dithiolene complexes have a remarkable set of properties, a fact which has made them the object of intense study for new materials and sensors.
The series Structure and Bonding publishes critical reviews on topics of research concerned with chemical structure and bonding. The scope of the series spans the entire Periodic Table and addresses structure and bonding issues associated with all of the elements. It also focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus is on the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processes are also relevant. The individual volumes in the series are thematic. The goal of each volume is to give the reader, whether at a university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to a larger scientific audience. Thus 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 should be presented using selected examples to illustrate the principles discussed. A description of the physical basis of the experimental techniques that have been used to provide the primary data may also be appropriate, if it has not been covered in detail elsewhere. The coverage need not be exhaustive in data, but should rather be conceptual, concentrating on the new principles being developed that will allow the reader, who is not a specialist in the area covered, to understand the data presented. Discussion of possible future research directions in the area is welcomed. Review articles for the individual volumes are invited by the volume editors. Readership: research scientists at universities or in industry, graduate students Special offer For all customers who have a standing order to the print version of Structure and Bonding, we offer free access to the electronic volumes of the Series published in the current year via SpringerLink.
Joseph Chatt was a pioneering figure in coordination chemistry. Intended as a record of Chatt's life, work, and influence, this book begins with a description of Chatt's career presented by co-workers, contemporaries, and students, then goes on to show that many of today's leading practitioners in the field have been influenced by Chatt. The latest research in coordination chemistry is presented to highlight Chatt's continuing legacy, in sections on the synthesis and reactivity of hydrido and dihydrogen complexes, the chemistry of phosphines, transition metal complexes of olefins and related isolobal ligands, chemistry related to dinitrogen complexes, the biological work of the ARC unit of nitrogen fixation at the University of Sussex, and patterns and generalizations in stability and reactivity. Leigh is affiliated with the University of Sussex, UK, and Winterton is affiliated with the University of Liverpool, UK. The book is distributed in the US by Springer Verlag. Annotation copyrighted by Book News Inc., Portland, OR.
This book focuses on the drug discovery and development applications of transition metal catalyzed processes, which can efficiently create preclinical and clinical drug candidates as well as marketed drugs. The authors pay particular attention to the challenges of transitioning academically-developed reactions into scalable industrial processes. Additionally, the book lays the groundwork for how continued development of transition metal catalyzed processes can deliver new drug candidates. This work provides a unique perspective on the applications of transition metal catalysis in drug discovery and development – it is a guide, a historical prospective, a practical compendium, and a source of future direction for the field.
Essentials of Organic Chemistry is an accessible introduction to the subject for students of Pharmacy, Medicinal Chemistry and Biological Chemistry. Designed to provide a thorough grounding in fundamental chemical principles, the book focuses on key elements of organic chemistry and carefully chosen material is illustrated with the extensive use of pharmaceutical and biochemical examples. In order to establish links and similarities the book places prominence on principles and deductive reasoning with cross-referencing. This informal text also places the main emphasis on understanding and predicting reactivity rather than synthetic methodology as well as utilising a mechanism based layout and featuring annotated schemes to reduce the need for textual explanations. * tailored specifically to the needs of students of Pharmacy Medical Chemistry and Biological Chemistry * numerous pharmaceutical and biochemical examples * mechanism based layout * focus on principles and deductive reasoning This will be an invaluable reference for students of Pharmacy Medicinal and Biological Chemistry.