Reactions of bis(diethyldithiocarbamato)oxomolybdenum(IV)

Abstract

The title compound, [MoO(S₂CNEt₂)₂], abstracts an oxygen atom from the following compounds and is oxidised to the molybdenum(VI) compound [MoO₂(S₂CNEt₂)₂]: oxygen; pyridine N-oxide; dimethyl sulphoxide, triphenylphosphine oxide; t-butyl nitrate; and tetraethylammonium nitrate. With dinitrogen mono-oxide and azoxybenzene the product is the molybdenum(V) compound, [Mo₂O₃(S₂CNEt₂)₄]. With benzohydrazide the product is a binuclear molybdenum(V) compound, [Mo₂(NH₂NHCOPh)₂O₂S₂(S₂CNEt₂)₂]. The preceding reactions are oxidative additions. In the presence of triphenylphosphine or triphenylphosphine sulphide a valency disproportionation occurs to the molybdenum(III) compound [Mo₂(S₂CNEt₂)₆] and the molybdenum(V) compound [Mo₂O₄(S₂CNEt₂)₂]. With the dithiocarbamato-compounds of molybdenum facile redox equilibria are established for the oxidation states III to VI involving both electron and oxygen-atom transfer.