Density functional theory gas- and solution-phase study of nucleophilic substitution at di- and trisulfides

Steven M. Bachrach, Joseph M. Hayes, Trang Dao, Justin Lee Mynar

    Research output: Contribution to journalArticlepeer-review

    29 Scopus citations

    Abstract

    Density functional calculations indicate that nucleophilic substitution in the thiolate-disulfide and thiolate-trisulfide exchange reactions proceeds by an addition-elimination pathway. Solution calculations were performed using B3LYP/6-31 + G* and the polarized continuum method. These solution-phase calculations indicate that for the reactions where the sulfur under attack bears a hydrogen atom, the substitution proceeds via an addition-elimination mechanism; however, when a methyl group is attached to the sulfur under attack, the SN2 mechanism is predicted.

    Original languageEnglish (US)
    Pages (from-to)266-271
    Number of pages6
    JournalTheoretical Chemistry Accounts
    Volume107
    Issue number5
    DOIs
    StatePublished - Jan 1 2002

    Keywords

    • DFT
    • Disulfide
    • Nucleophilic substitution
    • Solvent effects
    • Trisulfide

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry

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