Rapid, covalent addition of phosphine to dithiolene in a molybdenum tris(dithiolene). A new structural model for dimethyl sulfoxide reductase.
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.
Department of Chemistry, University of Toronto, Toronto, Ontario, Canada M5S 3H6.
Neilson
N
Nguyen
Alan J
AJ
Lough
Ulrich
U
Fekl
D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007506:Iron-Sulfur Proteins / Q000737:chemistry* / Q000378:metabolism; D008958:Models, Molecular; D015394:Molecular Structure; D010088:Oxidoreductases / Q000737:chemistry* / Q000378:metabolism; D010720:Phosphines / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D056831:Coordination Complexes; D007506:Iron-Sulfur Proteins; D010720:Phosphines; D013438:Sulfhydryl Compounds; D010088:Oxidoreductases; C045664:dimethyl sulfoxide reductase; C044646:phosphine