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

doi:10.1002/chem.201803431

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

4 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	15190-15194
Number of pages	5
Journal	Chemistry - A European Journal
Volume	24
Issue number	57
DOIs	https://doi.org/10.1002/chem.201803431
Publication status	Published - 2018 Oct 12

All Science Journal Classification (ASJC) codes

Catalysis
Organic Chemistry

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@article{2054ba68f18245a4b6ac9fb87cc71266,

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

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.",

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

note = "Funding Information: This work was supported by the Ministry of Science and Technology in Taiwan (MOST 106–2113-M-006-001 and MOST 105-2113-M-006-017-MY2). We thank Mr. Ming-Feng Chen at the Instrument Development Center at National Cheng Kung University for the ESI-MS measurements. Funding Information: This work was supported by the Ministry of Science and Technology in Taiwan (MOST 106?2113-M-006-001 and MOST 105-2113-M-006-017-MY2). We thank Mr. Ming-Feng Chen at the Instrument Development Center at National Cheng Kung University for the ESI-MS measurements. Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2018",

month = oct,

day = "12",

doi = "10.1002/chem.201803431",

language = "English",

volume = "24",

pages = "15190--15194",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "57",

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TY - JOUR

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

N1 - Funding Information: This work was supported by the Ministry of Science and Technology in Taiwan (MOST 106–2113-M-006-001 and MOST 105-2113-M-006-017-MY2). We thank Mr. Ming-Feng Chen at the Instrument Development Center at National Cheng Kung University for the ESI-MS measurements. Funding Information: This work was supported by the Ministry of Science and Technology in Taiwan (MOST 106?2113-M-006-001 and MOST 105-2113-M-006-017-MY2). We thank Mr. Ming-Feng Chen at the Instrument Development Center at National Cheng Kung University for the ESI-MS measurements. Publisher Copyright: © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2018/10/12

Y1 - 2018/10/12

N2 - 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.

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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U2 - 10.1002/chem.201803431

DO - 10.1002/chem.201803431

M3 - Article

C2 - 30024060

AN - SCOPUS:85053067094

SN - 0947-6539

VL - 24

SP - 15190

EP - 15194

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 57

ER -

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

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