engleski

New Molybdenum(V) Complexes Prepared by the Oxidation of Dinuclear Quadruply- Bonded Molybdenum(II) Monothiocarboxylates

Oxidation of molybdenum(II) thiopivalate and thiobenzoate in the presence of gama-picoline or pyridine results in the formation of dinuclear molybdenum(V) complexes of the general formulae [Mo_2O_2(mi-O)_2(mi-SO_4)L_4] with L = gama-picoline or pyridine and [Mo_2O_2(mi-O)(mi-S)(mi-SO_4)L_4] with L = gama-picoline. As determined by X-ray structure analysis two complexes with gama-picoline differ in their bridging cores: in one two Mo atoms are doubly bridged through two oxygen, in the other one through oxygen and sulfur atoms. However, they both crystallize together. The product is solvated with gama-picoline and water molecules. Molybdenum atoms exhibit distorted octahedral coordinations. The same complexes were prepared also through direct reactions of [Mo_2O_3(O_2CCH_3)_4] with thiopivalic and thiobenzoic acid in the presence of gama-picoline or pyridine. The appearance of the oxo-oxygens and sulfido-sulfur as well as sulfato ligand is explained by the molybdenum catalyzed oxidation of thiocarboxylates.

Crystal structure; oxomolybdenum(V) complexes; oxidation of molybdenum(II) complexes; catalysis

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