A computational mechanistic study of the cleavage of sulfur-sulfur bond by Frustrated Lewis Pairs

Lei Qin; Zhaoyin Zhang; Ruiqin Liu; Ming Zhou; Lili Zhao

doi:10.1016/j.tetlet.2023.154411

A computational mechanistic study of the cleavage of sulfur-sulfur bond by Frustrated Lewis Pairs

Lei Qin, Zhaoyin Zhang, Ruiqin Liu, Ming Zhou, Lili Zhao

School of Chemistry and Moleculai Engineering

Nanjing Tech University

Research output: Contribution to journal › Review article › peer-review

4 Scopus citations

Abstract

DFT calculations were performed to gain insight into the detailed mechanism of S[sbnd]S bond cleavage in disulfides (i.e., iPrSSiPr) by a frustrated Lewis pair (FLP) (tBu)₃P/B(C₆F₅)₃. The calculations revealed that the reaction initiates from the generation of weak complex B(C₆F₅)₃/iPrSSiPr (IM1) between iPrSSiPr and Lewis acid B(C₆F₅)₃. Subsequently, the Lewis base (tBu)₃P can activates the S[sbnd]S bond leading to the final cleavage of S[sbnd]S bond to give the product [(tBu)₃P(SiPr)][(iPrS)B(C₆F₅)₃] (PR). The computed kinetics and thermodynamics suggest that the reaction can take place reversibly under ambient conditions, which accounts well for the experimental observations. Furthermore, the mechanism is compared with that of the H[sbnd]H bond cleavages by same FLP. Contrast to the H[sbnd]H bond cleavage, a weak donor–acceptor complex IM1 between iPrSSiPr and B(C₆F₅)₃ could be located before S[sbnd]S bond cleavage. Nonetheless, the complete S[sbnd]S bond cleavage essentially is still due to the synergistic catalytic Lewis acid/base effects of FLP (tBu)₃P/B(C₆F₅)₃.

Original language	English
Article number	154411
Journal	Tetrahedron Letters
Volume	119
DOIs	https://doi.org/10.1016/j.tetlet.2023.154411
State	Published - 12 Apr 2023

Keywords

DFT calculations
Disulfides
Frustrated Lewis Pair (FLP)
NBO
Reaction mechanism
S[sbnd]S Bond cleavage

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10.1016/j.tetlet.2023.154411

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title = "A computational mechanistic study of the cleavage of sulfur-sulfur bond by Frustrated Lewis Pairs",

abstract = "DFT calculations were performed to gain insight into the detailed mechanism of S[sbnd]S bond cleavage in disulfides (i.e., iPrSSiPr) by a frustrated Lewis pair (FLP) (tBu)3P/B(C6F5)3. The calculations revealed that the reaction initiates from the generation of weak complex B(C6F5)3/iPrSSiPr (IM1) between iPrSSiPr and Lewis acid B(C6F5)3. Subsequently, the Lewis base (tBu)3P can activates the S[sbnd]S bond leading to the final cleavage of S[sbnd]S bond to give the product [(tBu)3P(SiPr)][(iPrS)B(C6F5)3] (PR). The computed kinetics and thermodynamics suggest that the reaction can take place reversibly under ambient conditions, which accounts well for the experimental observations. Furthermore, the mechanism is compared with that of the H[sbnd]H bond cleavages by same FLP. Contrast to the H[sbnd]H bond cleavage, a weak donor–acceptor complex IM1 between iPrSSiPr and B(C6F5)3 could be located before S[sbnd]S bond cleavage. Nonetheless, the complete S[sbnd]S bond cleavage essentially is still due to the synergistic catalytic Lewis acid/base effects of FLP (tBu)3P/B(C6F5)3.",

keywords = "DFT calculations, Disulfides, Frustrated Lewis Pair (FLP), NBO, Reaction mechanism, S[sbnd]S Bond cleavage",

author = "Lei Qin and Zhaoyin Zhang and Ruiqin Liu and Ming Zhou and Lili Zhao",

note = "Publisher Copyright: {\textcopyright} 2023 Elsevier Ltd",

year = "2023",

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day = "12",

doi = "10.1016/j.tetlet.2023.154411",

language = "英语",

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T1 - A computational mechanistic study of the cleavage of sulfur-sulfur bond by Frustrated Lewis Pairs

AU - Qin, Lei

AU - Zhang, Zhaoyin

AU - Liu, Ruiqin

AU - Zhou, Ming

AU - Zhao, Lili

PY - 2023/4/12

Y1 - 2023/4/12

N2 - DFT calculations were performed to gain insight into the detailed mechanism of S[sbnd]S bond cleavage in disulfides (i.e., iPrSSiPr) by a frustrated Lewis pair (FLP) (tBu)3P/B(C6F5)3. The calculations revealed that the reaction initiates from the generation of weak complex B(C6F5)3/iPrSSiPr (IM1) between iPrSSiPr and Lewis acid B(C6F5)3. Subsequently, the Lewis base (tBu)3P can activates the S[sbnd]S bond leading to the final cleavage of S[sbnd]S bond to give the product [(tBu)3P(SiPr)][(iPrS)B(C6F5)3] (PR). The computed kinetics and thermodynamics suggest that the reaction can take place reversibly under ambient conditions, which accounts well for the experimental observations. Furthermore, the mechanism is compared with that of the H[sbnd]H bond cleavages by same FLP. Contrast to the H[sbnd]H bond cleavage, a weak donor–acceptor complex IM1 between iPrSSiPr and B(C6F5)3 could be located before S[sbnd]S bond cleavage. Nonetheless, the complete S[sbnd]S bond cleavage essentially is still due to the synergistic catalytic Lewis acid/base effects of FLP (tBu)3P/B(C6F5)3.

AB - DFT calculations were performed to gain insight into the detailed mechanism of S[sbnd]S bond cleavage in disulfides (i.e., iPrSSiPr) by a frustrated Lewis pair (FLP) (tBu)3P/B(C6F5)3. The calculations revealed that the reaction initiates from the generation of weak complex B(C6F5)3/iPrSSiPr (IM1) between iPrSSiPr and Lewis acid B(C6F5)3. Subsequently, the Lewis base (tBu)3P can activates the S[sbnd]S bond leading to the final cleavage of S[sbnd]S bond to give the product [(tBu)3P(SiPr)][(iPrS)B(C6F5)3] (PR). The computed kinetics and thermodynamics suggest that the reaction can take place reversibly under ambient conditions, which accounts well for the experimental observations. Furthermore, the mechanism is compared with that of the H[sbnd]H bond cleavages by same FLP. Contrast to the H[sbnd]H bond cleavage, a weak donor–acceptor complex IM1 between iPrSSiPr and B(C6F5)3 could be located before S[sbnd]S bond cleavage. Nonetheless, the complete S[sbnd]S bond cleavage essentially is still due to the synergistic catalytic Lewis acid/base effects of FLP (tBu)3P/B(C6F5)3.

KW - DFT calculations

KW - Disulfides

KW - Frustrated Lewis Pair (FLP)

KW - NBO

KW - Reaction mechanism

KW - S[sbnd]S Bond cleavage

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U2 - 10.1016/j.tetlet.2023.154411

DO - 10.1016/j.tetlet.2023.154411

M3 - 文献综述

AN - SCOPUS:85148894511

SN - 0040-4039

VL - 119

JO - Tetrahedron Letters

JF - Tetrahedron Letters

M1 - 154411

ER -

A computational mechanistic study of the cleavage of sulfur-sulfur bond by Frustrated Lewis Pairs

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Keywords

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