Activation of O-H and C-O Bonds in Water and Methanol by a Vanadium-Bound Thiyl Radical.

The reaction of [V(PS3")] (1) (PS3"=[P(C H -3-Me Si-2-S) ] ) with H O led to the formation of [V (PS3")(PS2"S )] (2) (PS2"S =[P(C H -3-Me Si-2-S) (C H -3-Me Si-2-SH)] ), indicating a hydrogen atom transfer from H O to a bound thiolate in 1. Furthermore, the reaction of 1 with CH OH gave the generation of complexes 2 and 3, [V (PS3")(PS2"S )] (PS2"S =[P(C H -3-Me Si-2-S) (C H -3-Me Si-2-SCH )] ), implying that C-O and O-H bonds are cleaved by 1. Quantum mechanical calculations were performed to provide the mechanistic understanding for the reactivity of 1 with water.