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Synthesis, Structure, and Reactivity of Novel Dithiolato(oxo)rhenium(V) Complexes.

Oxygen atom transfer catalyzed by transition metal complexes holds great interest owing to its chemical and biological relevance. The intriguing mechanisms of certain of these reactions catalyzed by organorhenium oxides have been revealed. As the authors became involved in certain sulfur atom transfer reactions, it became important to synthesize stable thiolato complexes derived from methyltrioxorhenium (CH{sub 3}ReO{sub 3} or MTO), in that they are related to important catalytic intermediates. A tetrathiophenylato complex, unstable above 15 C, has been reported, as have anionic dithiolato complexes of rhenium(V)-sulfides. Prompted by these reports, the authors sought to prepare new, thermally stable thiolato complexes derived from MTO. They have synthesized, analyzed, and characterized new oxorhenium(V) complexes containing a dithiolato ligand. The dinuclear version of this complex is monomerized upon reaction with triphenylphosphine. The dimer readily reacts with several O-atom donors, undergoing oxidation both at the metal and at the ligand. They are currently investigating the scope and mechanism of this reaction and further studying the reactivity of this binuclear complex.