Reduction of tris(benzene-1,2-dithiolate)molybdenum(VI) by water. A functional mo-hydroxylase analogue system.
Mo(VI)(S(2)C(6)H(4))(3) reacts cleanly and completely with H(2)O in THF to afford [H(3)O](+)[Mo(V)(S(2)C(6)H(4))(3)](-). Kinetic data were fit by the rate equation -d[Mo(VI)(S(2)C(6)H(4))(3)]/dt = k[Mo(VI)(S(2)C(6)H(4))(3)]/[H(3)O(+)], which is consistent with a coupled electron-proton transfer mechanism involving a coordinated H(2)O molecule. The Mo(VI)(S(2)C(6)H(4))(3) reduction is accelerated by the presence of PPh(3) and affords OPPh(3). (18)O isotope tracing shows that H(2)O is the source of oxygen transferred to PPh(3).
Cervilla
Antonio
A
ICMUV, P.O. Box 2085, Polígono La Coma, Paterna, Valencia 46071, Spain. Antonio.cervilla@uv.es
Pérez-Pla
Francisco
F
Llopis
Elisa
E
Piles
María
M
D006899:Mixed Function Oxygenases / Q000737:chemistry / Q000378:metabolism*; D008956:Models, Chemical; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D014867:Water / Q000737:chemistry
D009942:Organometallic Compounds; D014867:Water; D008982:Molybdenum; D006899:Mixed Function Oxygenases