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

Jyun An Yan, Zi Kuan Yang, Yu Sen Chen, Ya Ho Chang, Chiao Ling Lyu, Chun Gang Luo, Mu Jeng Cheng, Hua Fen Hsu

Research output: Contribution to journalArticlepeer-review

4 Citations (Scopus)


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.

Original languageEnglish
Pages (from-to)15190-15194
Number of pages5
JournalChemistry - A European Journal
Issue number57
Publication statusPublished - 2018 Oct 12

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry


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