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The reaction of alkyl hydropersulfides (RSSH, R = CH3 and tBu) with H2S in the gas phase and in aqueous solution

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Abstract

The RSSH + H2S → RSH + HSSH reaction has been suggested by numerous labs to be important in H2S-mediated biological processes. Seven different mechanisms for this reaction (R = CH3, as a model) have been studied using the DFT methods (M06-2X and ωB97X-D) with the Dunning aug-cc-pV(T+d)Z basis sets. The reaction of CH3SSH with gas phase H2S has a very high energy barrier (>45 kcal mol−1), consistent with the available experimental observations. A series of substitution reactions R1–S–S–H + S–R2 (R1 = Me, tBu, Ad, R2 = H, S–Me, S–tBu, S–Ad) have been studied. The regioselectivity is largely affected by the steric bulkiness of R1, but is much less sensitive to R2. Thus, when R1 is Me, all S–R2 favorably attack the internal S atom, leading to R1–S–S–R2. While for R1 = tBu, Ad, all S–R2 significantly prefer to attack the external S atom to form S–S–R2. These results are in good agreement with the experimental observations.

Graphical abstract: The reaction of alkyl hydropersulfides (RSSH, R = CH3 and tBu) with H2S in the gas phase and in aqueous solution

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Publication details

The article was received on 30 Aug 2018, accepted on 28 Sep 2018 and first published on 28 Sep 2018


Article type: Paper
DOI: 10.1039/C8CP05503C
Citation: Phys. Chem. Chem. Phys., 2019, Advance Article
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    The reaction of alkyl hydropersulfides (RSSH, R = CH3 and tBu) with H2S in the gas phase and in aqueous solution

    L. Zhang, X. Zhang, Y. Wu, Y. Xie, J. M. Fukuto and H. F. Schaefer, Phys. Chem. Chem. Phys., 2019, Advance Article , DOI: 10.1039/C8CP05503C

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