Rapid, covalent addition of phosphine to dithiolene in a molybdenum tris(dithiolene). A new structural model for dimethyl sulfoxide reductase |
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Authors: | Nguyen Neilson Lough Alan J Fekl Ulrich |
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Institution: | Department of Chemistry, University of Toronto, Toronto, Ontario, Canada M5S 3H6. |
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Abstract: | Triphenylphosphine (PPh(3)) rapidly and reversibly adds to the bdt ligand in the molybdenum tris(dithiolene) complex Mo(tfd)(2)(bdt) tfd = S(2)C(2)(CF(3))(2); bdt = S(2)C(6)H(4)], turning chelating bdt into the monodentate zwitterionic ligand SC(6)H(4)SPPh(3). A second PPh(3) molecule fills the newly created open site in the crystallographically characterized product Mo(tfd)(2)(SC(6)H(4)SPPh(3))(PPh(3)), which is a structural model for dimethyl sulfoxide (DMSO) reductase. While the complex is only a precatalyst for reduction of DMSO by PPh(3) (the initially low catalytic rate increases with time), Mo(tfd)(2)(SMe(2))(2) was found to be catalytically active without an induction period. |
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