Synthesis and characterization of binuclear oxomolybdenum(V) and dioxomolybdenum(VI) O,O '-ditolyl dithiophosphate complexes. Crystal structures of Mo2O3[S2P(OC6H4Me-o)(2)](4), Mo2O3[S2P(OC6H4Me-m)(2)](4) and MoO2[S2P(OC6H4Me-p)(2)](2)

摘要

A series of binuclear oxomolybdenum(V) O,O'-ditolyl dithiophosphate complexes, Mo2O3[S2P(OR)(2)](4) (R = o-, m-, p-C6H4Me) were synthesized by drop wise addition of aqueous solution of the ammonium salt of O,O'-ditolyl dithiophosphoric acid into an acidic solution of sodium molybdate with constant stirring to yield purple solids. Dioxomolybdenum(VI) O,O'-ditolyl dithiophospbate complexes, MoO2[S2P(OR)(2)](2) (R = o-, m-, p-C6H4Me and CH2C6H5) were also synthesized by reducing Mo2O3[S2P(OR)(2)](4) with OPPh3 in benzene to yield yellow solids. These complexes were characterized by elemental analysis and IR, H-1 and P-31 NMR spectroscopy and, in three cases, by X-ray crystallography. In Mo2O3[S2P(OC6H4Me-o)(2)](4) and Mo2O3[S2P(OC6H4Me-m)(2)](4), the environment around each molybdenum atom can be described as the expected distorted octahedral, consisting of one terminal and one bridging oxygen along with the four chelating sulfur atoms of the dithio ligands, with one Mo-S distance being significantly longer than the other three. In MoO2[S2P(OC6H4Me-p)(2)](2) the geometry around the Mo atom is again distorted octahedral with two cis terminal oxygen atoms and two anisobidentate dithiophosphate ligands. (c) 2007 Elsevier Ltd. All rights reserved.