Inorganic Chemistry, Vol.51, No.12, 6446-6448, 2012
Rapid, Covalent Addition of Phosphine to Dithiolene in a Molybdenum Tris(dithiolene). A New Structural Model for Dimethyl Sulfoxide Reductase
Triphenylphosphine (PPh3) rapidly and reversibly adds to the bdt ligand in the molybdenum tris(dithiolene) complex Mo(tfd)(2)(bdt) [tfd = S2C2(CF3)(2); bdt = S2C6H4], turning chelating bdt into the monodentate zwitterionic ligand SC6H4SPPh3. A second PPh3 molecule fills the newly created open site in the crystallographically characterized product Mo(tfd)(2)(SC6H4SPPh3)(PPh3), which is a structural model for dimethyl sulfoxide (DMSO) reductase. While the complex is only a precatalyst for reduction of DMSO by PPh3 (the initially low catalytic rate increases with time), Mo(tfd)(2)(SMe2)(2) was found to be catalytically active without an induction period.