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

Mo^VI(S₂C₆H₄)₃ reacts cleanly and completely with H₂O in THF to afford [H₃O]⁺[Mo^V(S₂C₆H₄)₃]^-. Kinetic data were fit by the rate equation −d[Mo^VI(S₂C₆H₄)₃]/dt = k[Mo^VI(S₂C₆H₄)₃]/[H₃O⁺], which is consistent with a coupled electron−proton transfer mechanism involving a coordinated H₂O molecule. The Mo^VI(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.