MOLYBDENUM(V) COMPLEXES WITH MONOTHIO-BETA-DIKETONES - THIODIPIVALOYLMETHANE, THIODIBENZOYLMETHANE AND BENZOYLTHIOACETONE

The preparations of oxomolybdenum(V) complexes with thiodipivaloylmethane (Htdpm), [Mo2O3-(tdpm)4] 1 and [But2C3HS2][MoO(SH)3(tdpm)] 2, thiodibenzoylmethane (Htdbm), [Mo2O3(tdpm)4] 3, and both benzoylacetone (Hba) and benzoylthioacetone (Hbta), [Mo2O3(ba)3(bta)] 4, are described. Crystal structures of 1 and 2 have been determined by X-ray diffraction techniques. Complex 1 is dinuclear, the anion of 2 mononuclear, both containing the molybdenum atoms in distorted-octahedral geometry The charge transfer between the cation and anion of 2 is associated with close contacts between both the dithiolylium sulfurs and the SH-sulfur atom S(3) [S...S 3.335(2) and 3.515(2) angstrom].