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

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4 引文斯高帕斯（Scopus）

摘要

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.

原文	English
頁（從 - 到）	15190-15194
頁數	5
期刊	Chemistry - A European Journal
卷	24
發行號	57
DOIs	https://doi.org/10.1002/chem.201803431
出版狀態	Published - 2018 10月 12

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有機化學

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10.1002/chem.201803431

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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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