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 journalArticle

Abstract

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
Volume24
Issue number57
DOIs
Publication statusPublished - 2018 Oct 12

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Vanadium
Carbon Monoxide
Methanol
Chemical activation
Water
Sulfur
Hydrogen
Metals
Atoms
Kinetics

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Yan, Jyun An ; Yang, Zi Kuan ; Chen, Yu Sen ; Chang, Ya Ho ; Lyu, Chiao Ling ; Luo, Chun Gang ; Cheng, Mu-Jeng ; Hsu, Hua-Fen. / Activation of O−H and C−O Bonds in Water and Methanol by a Vanadium-Bound Thiyl Radical. In: Chemistry - A European Journal. 2018 ; Vol. 24, No. 57. pp. 15190-15194.
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Activation of O−H and C−O Bonds in Water and Methanol by a Vanadium-Bound Thiyl Radical. / Yan, Jyun An; Yang, Zi Kuan; Chen, Yu Sen; Chang, Ya Ho; Lyu, Chiao Ling; Luo, Chun Gang; Cheng, Mu-Jeng; Hsu, Hua-Fen.

In: Chemistry - A European Journal, Vol. 24, No. 57, 12.10.2018, p. 15190-15194.

Research output: Contribution to journalArticle

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T1 - Activation of O−H and C−O Bonds in Water and Methanol by a Vanadium-Bound Thiyl Radical

AU - Yan, Jyun An

AU - Yang, Zi Kuan

AU - Chen, Yu Sen

AU - Chang, Ya Ho

AU - Lyu, Chiao Ling

AU - Luo, Chun Gang

AU - Cheng, Mu-Jeng

AU - Hsu, Hua-Fen

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AB - 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.

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