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The chemistry of molybdenum is immensely rich and diverse. Molybdenum is essential for life, and has many applications in industry. The first chapter offers a general perspective of the chemistry of molybdenum in high oxidation states dominated by diverse oxo species, such as the MoO22+ and MoO4+ units that are focus of my research. I describe the importance of MoO22+ complexes as models for the active sites of oxo transfer molybdoenzymes (e.g. DMSO oxidase) and for industrial heterogeneous transformation such as the SOHIO process (one of our ultimate goals). I also outline the importance of MoO4+ complexes as procatalysts for metathesis polymerization and as models of deoxygenated active sites of MoO22+ oxygen catalysts that have triggered our interest. The second chapter introduces the synthesis and full characterization of 4-, 5- and 6-coordinated MoO2(OAr)2L0-1 complexes with bulky aryloxide ligands, starting from the MoO2Cl2 or MoO2Cl2(DMF)2 precursors. Steric and electronic modifications in the aryloxide moieties were performed in order to understand their effect in the final structure and yields of the synthesized complexes. The nature and mechanism of formation of the radical species detected in their synthesis is proposed. The third chapter presents the facile synthesis of varios MoO(OAr)4-nCln complexes starting from the MoO2Cl2 precursor. Their mechanism of formation is proposed and the supporting evidence for this new reaction is provided. Steric and electronic modifications in the aryloxide moieties were used to study their structural and electronic effects in the MoO4+ complexes. The fourth chapter outlines the synthesis of Mo(VI) monooxo bisphenoxides with a characteristic cis-chloro cis-bisphoxide arrangement around the MoO4+ unit. Electronic and steric modifications in the bisphenoxide rings were done to determine their effect in the structure and reactivity of the final complexes. The fifth chapter introduces the application of the synthesized MoO(OAr)4-nCln and MoO(bisphenoxides)2Cl2 complexes as procatalysts for olefin metathesis polymerization of norbornene. The correlation between structure and reactivity of the procatalyst is discussed.
In retrospect, it was obvious that we were both, quite inde pendently, contemplating a conference on the role of molybdenum in biology and related chemistry. At the time though, the meeting of minds on this matter was quite surprising. Although this subject has been treated in previous meetings within the overall context of, say, magnetic resonance or nitrogen fixation, it was apparent to us both that research in molybdenum-containing enzymes and molyb denum chemistry had progressed rapidly in the last several years. Jointly, we decided to organize the first meeting on Molybdenum Chemistry of Biological Significance which was held at the Hotel Lake Biwa, Shiga, Japan, on April 10-13, 1979. This volume con stitutes the Proceedings of that international conference and covers the broad spectrum of interests from enzymes to coordination chemistry. It should serve not only as a source of new information on the latest research results in this area and as a useful ref erence tool, but should also allow a newcomer or other peripherally interested researcher to become conversant very rapidly with the "state-of-the-art" in this specialized and important area of research. The conference was sponsored by the Japan Society for the Promotion of Science, the Japan World Exposition Commemerative Fund the Yamada Science Foundation, the Nissan Science Foundation, the Chemical Society of Japan (Kinki Regional Office) and the Agri cultural Chemical Society of Japan (Kansai Branch). We thank these organizations sincerely for their interest and generosity.
Molybdenum is an element with an extremely rich and interesting chemistry having very versatile applications in various fields of human activity. It is used extensively in metallurgical applications. Because of their anti-wear properties, molybdenum compounds find wide applications as lubricants - particularly in extreme or hostile environmental situations. Many molybdates and heteropolymolybdates are white and therefore used as pigments. In addition, they are non-toxic and act as efficient corrosion inhibitors and smoke suppressants. Hydroprocessing of petroleum is one of the largest industries employing heterogeneous catalysts. Molybdenum catalysts have shown great promise in the liquefaction of coal and this may develop into one of its most important catalytic uses. The use of molybdenum compounds in homogeneous catalysis is also significant. Three important classes of molybdenum compounds in the solid state are reviewed, viz., oxides, sulphides and halides. The role of molybdenum in inorganic catalysis and enzymes receives prominent mention because of their impact on the progress of science and technology. Further biochemical and enzymic factors are discussed in separate chapters and their reaction to agriculture and animal husbandry. A new classification of covalent compounds which abandons the traditional oxidation state concept allows a powerful approach to the organisation of the complex and rich chemistry of molybdenum. Dramatic colour diagrams of abundances of molybdenum compounds provide broad insights into the important features and trends in the chemistry of molybdenum including reactivity and mechanism. The book is intended for use mainly as a research monograph by the many workers who may encounter molybdenum chemistry or who are looking for its application and potential uses in different technological fields. However, it will also serve as an advanced text for university lecturers and postgraduate students interested in inorganic, physical and industrial chemistry, chemical technology or biochemistry and biotechnology.
There has been enormous progress in our understanding of molybdenum and tungsten enzymes and relevant inorganic complexes of molybdenum and tungsten over the past twenty years. This set of three books provides a timely and comprehensive overview of the field and documents the latest research. Building on the first volume that focussed on biochemistry aspects, the second volume in the set focusses on the inorganic complexes that model the structures and reactivity of the active sites of each major group of molybdenum and tungsten enzymes. Special attention is given to synthetic strategies, reaction mechanism and chemical kinetics of these systems. The introductory chapter provides a useful overview and places the topic of the book into a wider context. This text will be a valuable reference to workers both inside and outside the field, including graduate students and young investigators interested in developing new research programs in this area.
Molybdenum and Molybdenum-Containing Enzymes is a collection of papers that deals with the various concerns with molybdenum-containing enzymes. The text first covers the organometallic chemistry of molybdenum, and then proceeds to tackling molybdenum-containing enzymes, such as xanthine oxidase, aldehyde oxidase, and sulphite oxidase. The text also discusses the advancement in the understanding of molybdenum-containing enzymes. The remaining chapters deal with the genetics of molybdoenzymes and the nutritional aspects of molybdenum. The book will be of great use to students, researchers, and practitioners of biochemistry.
Volume 7 in the Metal Ions in Biology Series, divided into two parts, covers the nitrogenase enzyme complex and the molybdenum redox enzymes. Part one covers the chemistry of Mo-Fe-S clusters and their relationship to nitrogenase, cofactor chemistry and biochemistry of nitrogenase, spectroscopic and electrochemical studies of the Fe-Mo cofactor and Fe-S clusters, and more. Part Two surveys oxo-molybdenum chemistry, discusses the nature of the molybdo-pterin complex, and describes the characteristics of several of the Mo redox enzymes.