The reduction of tris-dithiolene complexes of molybdenum(VI) and tungsten(VI) by hydroxide ion: kinetics and mechanism

Dalton Transactions : an International Journal of Inorganic Chemistry
A CervillaMaría Piles

Abstract

The kinetic study of the spontaneous reduction of some neutral tris-dithiolene complexes [ML3] of molybdenum(VI) and tungsten(VI), (L = S2C6H4(2-), S2C6H3CH3(2-) and S2C2(CH3)2(2-); M = Mo or W) by tetrabutylammonium hydroxide in tetrahydrofuran-water solutions demonstrates that OH- is an effective reductant. Their reduction is fast, clean and quantitative. Depending upon both the molar ratio in which the reagents are mixed and the amount of water present, one- or two-electron reductions of these tris-dithiolene complexes were observed. If Bu4NOH is present in low concentration or/and at high concentrations of water, the total transformation of the neutral M(VI) complex into the monoanionic M(V) complex is the only observed process. Stopped-flow kinetic data for this reaction are consistent with the rate law: -d[ML3]/dt = d[ML3-]/dt = k[ML3][Bu4NOH]. The proposed mechanism involves nucleophilic attack of OH- to form a mono-anionic seven-coordinate intermediate [ML3OH]-, which interacts with another molecule of [ML3] to generate the monoanionic complex [ML3]- transfering the oxygen from coordinated OH- to water. Hydrogen peroxide was identified as the reaction product. The molybdenum complexes are more difficult to reduce than t...Continue Reading

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