Spectral Characterization of Three-Electron Two-Center (3e-2c) Bonds of Gaseous CH3S-S(H)CH3 and (CH3SH)2+ and Enhancement of the 3e-2c Bond upon Protonation

Min Xie; Zhitao Shen; Dandan Wang; Asuka Fujii; Yuan-Pern Lee

doi:10.1021/acs.jpclett.8b01491

Spectral Characterization of Three-Electron Two-Center (3e-2c) Bonds of Gaseous CH₃S-S(H)CH₃ and (CH₃SH)₂⁺ and Enhancement of the 3e-2c Bond upon Protonation

Min Xie^*, Zhitao Shen, Dandan Wang, Asuka Fujii, Yuan-Pern Lee

^*Corresponding author for this work

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

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Abstract

The three-electron two-center (3e-2c) bond plays an important role in structures and electron communication in biological systems involving cationic sulfur compounds. Although the nature of 3e-2c bonds and their theoretical formalism have attracted great interest, direct spectral identifications of 3e-2c-bound molecules are scarce. We observed the infrared spectra of the weakly 3e-2c-bound CH₃S-S(H)CH₃ and the strongly 3e-2c-bound (CH₃SH)₂⁺ in a supersonic jet using infrared (IR) dissociation with vacuum-ultraviolet photoionization and time-of-flight detection. Protonation of CH₃S-S(H)CH₃ to form [CH₃(H)S-S(H)CH₃]⁺ significantly enhances the 3e-2c bond, characterized by a large red shift of the SH-stretching band with enhanced IR intensity, shortening of the calculated S-S distance from 3.00 to 2.86 Å, and a dissociation energy increased from ∼23 to 162 kJ mol^-1.

Original language	English
Pages (from-to)	3725-3730
Number of pages	6
Journal	Journal of Physical Chemistry Letters
Volume	9
Issue number	13
DOIs	https://doi.org/10.1021/acs.jpclett.8b01491
State	Published - 5 Jul 2018

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title = "Spectral Characterization of Three-Electron Two-Center (3e-2c) Bonds of Gaseous CH3S-S(H)CH3 and (CH3SH)2+ and Enhancement of the 3e-2c Bond upon Protonation",

abstract = "The three-electron two-center (3e-2c) bond plays an important role in structures and electron communication in biological systems involving cationic sulfur compounds. Although the nature of 3e-2c bonds and their theoretical formalism have attracted great interest, direct spectral identifications of 3e-2c-bound molecules are scarce. We observed the infrared spectra of the weakly 3e-2c-bound CH3S-S(H)CH3 and the strongly 3e-2c-bound (CH3SH)2+ in a supersonic jet using infrared (IR) dissociation with vacuum-ultraviolet photoionization and time-of-flight detection. Protonation of CH3S-S(H)CH3 to form [CH3(H)S-S(H)CH3]+ significantly enhances the 3e-2c bond, characterized by a large red shift of the SH-stretching band with enhanced IR intensity, shortening of the calculated S-S distance from 3.00 to 2.86 {\AA}, and a dissociation energy increased from ∼23 to 162 kJ mol-1.",

author = "Min Xie and Zhitao Shen and Dandan Wang and Asuka Fujii and Yuan-Pern Lee",

year = "2018",

month = jul,

day = "5",

doi = "10.1021/acs.jpclett.8b01491",

language = "English",

volume = "9",

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journal = "Journal of Physical Chemistry Letters",

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T1 - Spectral Characterization of Three-Electron Two-Center (3e-2c) Bonds of Gaseous CH3S-S(H)CH3 and (CH3SH)2+ and Enhancement of the 3e-2c Bond upon Protonation

AU - Xie, Min

AU - Shen, Zhitao

AU - Wang, Dandan

AU - Fujii, Asuka

AU - Lee, Yuan-Pern

PY - 2018/7/5

Y1 - 2018/7/5

N2 - The three-electron two-center (3e-2c) bond plays an important role in structures and electron communication in biological systems involving cationic sulfur compounds. Although the nature of 3e-2c bonds and their theoretical formalism have attracted great interest, direct spectral identifications of 3e-2c-bound molecules are scarce. We observed the infrared spectra of the weakly 3e-2c-bound CH3S-S(H)CH3 and the strongly 3e-2c-bound (CH3SH)2+ in a supersonic jet using infrared (IR) dissociation with vacuum-ultraviolet photoionization and time-of-flight detection. Protonation of CH3S-S(H)CH3 to form [CH3(H)S-S(H)CH3]+ significantly enhances the 3e-2c bond, characterized by a large red shift of the SH-stretching band with enhanced IR intensity, shortening of the calculated S-S distance from 3.00 to 2.86 Å, and a dissociation energy increased from ∼23 to 162 kJ mol-1.

AB - The three-electron two-center (3e-2c) bond plays an important role in structures and electron communication in biological systems involving cationic sulfur compounds. Although the nature of 3e-2c bonds and their theoretical formalism have attracted great interest, direct spectral identifications of 3e-2c-bound molecules are scarce. We observed the infrared spectra of the weakly 3e-2c-bound CH3S-S(H)CH3 and the strongly 3e-2c-bound (CH3SH)2+ in a supersonic jet using infrared (IR) dissociation with vacuum-ultraviolet photoionization and time-of-flight detection. Protonation of CH3S-S(H)CH3 to form [CH3(H)S-S(H)CH3]+ significantly enhances the 3e-2c bond, characterized by a large red shift of the SH-stretching band with enhanced IR intensity, shortening of the calculated S-S distance from 3.00 to 2.86 Å, and a dissociation energy increased from ∼23 to 162 kJ mol-1.

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U2 - 10.1021/acs.jpclett.8b01491

DO - 10.1021/acs.jpclett.8b01491

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AN - SCOPUS:85048855131

VL - 9

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JO - Journal of Physical Chemistry Letters

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IS - 13

ER -

Spectral Characterization of Three-Electron Two-Center (3e-2c) Bonds of Gaseous CH₃S-S(H)CH₃ and (CH₃SH)₂⁺ and Enhancement of the 3e-2c Bond upon Protonation

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