The cocondensation reactions of molybdenum trioxide vapor with tetraalkoxysilanes, trimethylalkoxysilanes, and hexamethyldisiloxane at -196°C were investigated. The products from the metal vapor reactions of tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane were characterized as molybdenum(VI)dioxodialkoxy compounds. The isolated compounds were found to be polymeric in the solid state by bridging through alkoxide groups. Metal vapor reaction of trimethylmethoxysilane gave an inseparable mixture of molybdenum(VI)alkoxysiloxy compounds which were also polymeric in nature. The metal vapor reactions of tetra-2-butoxysilane and trimethyl-t-butoxysilane gave butenes as a primary organic product and an uncharacterized blue molybdenum-containing solid. All products isolated in this study were sensitive to atmospheric moisture and light. The molybdenumdioxoalkoxy and molybdenumdioxoalkoxysiloxy compounds are good model compounds for the oxidation of alcohols. Decomposition studies of Mo(0)2(OMe)2 and Mo(0)2(OMe)x(OSiMe3)y yielded oxidation products of methanol, including dimethylether, formaldehyde, methyl formate, and dimethoxymethane. The reactivity of Mo(0)2(OEt)2 towards acidic protons was used to attach the molybdenum(VI)dioxo group to the surface of alumina (Al203), silica (Si02), titania (Ti02), zirconia (Zr02), and HY-zeolite. Chemical analysis and infrared spectroscopic studies indicate that dioxomolybdenum is attached to the support through bridging oxides between the support metal and molybdenum. The +2, +4, and +6 oxidation states of the surface attached molybdenum could be accessed by oxidation or reduction with 02 or H2, respectively. A survey of the catalytic nature for oxidation, metathesis, and Fischer- Tropsch synthesis of the supported molybdenum compounds in appropriate oxidation states was made. Dramatic differences in the activity and selectivity for oxidation of alcohols were observed depending on the support used. The Ti02 supported Mo(VI) showed the highest activity and selectivity for the oxidation of methanol to formaldehyde. The A1203 supported Mo(IV) system was the most active catalyst for propylene metathesis with the Si02 supported Mo(IV) system showing much less activity.

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.