The reaction of [V(PS3“)]− (1) (PS3”=[P(C6H3-3-Me3Si-2-S)3]3−) with H2O led to the formation of [VIV(PS3“)(PS2”SH)]− (2) (PS2“SH=[P(C6H3-3-Me3Si-2-S)2(C6H3-3-Me3Si-2-SH)]2−), indicating a hydrogen atom transfer from H2O to a bound thiolate in 1. Furthermore, the reaction of 1 with CH3OH gave the generation of complexes 2 and 3, [VIV(PS3”)(PS2“SCH3)]− (PS2”SCH3=[P(C6H3-3-Me3Si-2-S)2(C6H3-3-Me3Si-2-SCH3)]2−), 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. A key transition state with a lower kinetic barrier is identified. It involves an O−H bond cleavage by a dissociated thiyl radical with an interaction between an OH group and a neighboring bound sulfur donor. To our knowledge, the reactivity of 1 represents a new mode for water activation conducted through cooperation between a metal-stabilized thiyl radical and a neighboring thiolato donor.
All Science Journal Classification (ASJC) codes
- Organic Chemistry