Reduction of Tris(benzene-1,2-dithiolate)molybdenum(VI) by Water. A Functional MoHydroxylase Analogue System

MoVI(S2C6H4)3 reacts cleanly and completely with H2O in THF to afford [H3O]+[MoV(S2C6H4)3]-. Kinetic data were fit by the rate equation -d[MoVI(S2C6H4)3]/dt = k[MoVI(S2C6H4)3]/[H3O+], which is consistent with a coupled electron-proton transfer mechanism involving a coordinated H2O molecule. The MoVI(S2C6H4)3 reduction is accelerated by the presence of PPh3 and affords OPPh3. 18O isotope tracing shows that H2O is the source of oxygen transferred to PPh3.