The reaction of [V(PS3“)]⁻ (1) (PS3”=[P(C₆H₃‐3‐Me₃Si‐2‐S)₃]³⁻) with H₂O led to the formation of [V^IV(PS3“)(PS2”S^H)]⁻ (2) (PS2“S^H=[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, [V^IV(PS3”)(PS2“S^CH3)]⁻ (PS2”S^CH3=[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.

中文翻译：

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钒结合的巯基自由基活化水和甲醇中的O-H和C-O键

的[V（PS3“）]的反应^-（1）（PS3” = [P（C ₆ H ^ ₃ -3-ME ₃的Si-2-S）₃ ] ^3-）用H ₂ O LED以形成[V ^IV（PS3”）（PS2” S ^H）] ⁻（2）（PS2“ S ^H = [P（C ₆ H ₃ -3-Me ₃ Si-2-S）₂（C ₆ H ₃ -3 -Me ₃的Si-2-SH）] ^2-），表明选自H氢原子转移₂ O操作绑定硫醇盐在1。此外，1与CH ₃ OH的反应产生了配合物 2和3，[V ^IV（PS3”）（PS2” S ^CH3）] ^-（PS2” S ^CH3 = [P（C ₆ H ₃ -3-我₃的Si-2-S）₂（C ₆ H ^ ₃ -3-ME ₃的Si-2-SCH ₃）] ^2-），这意味着C-O和O-H键由裂解1。进行了量子力学计算，以提供对1的反应性的力学理解。与水。确定了具有较低动力学势垒的关键过渡状态。它涉及通过离解的噻吩基进行的OH键裂解，OH基团与相邻的键合硫供体之间存在相互作用。据我们所知，1的反应性是通过金属稳定的硫代自由基与相邻的硫醇基供体之间的相互作用进行水活化的一种新模式。