Density functional theory gas- and solution-phase study of nucleophilic substitution at di- and trisulfides
Autor: | Justin L. Mynar, Joseph Hayes, Trang Dao, Steven M. Bachrach |
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Rok vydání: | 2002 |
Předmět: | |
Zdroj: | Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta). 107:266-271 |
ISSN: | 1432-2234 1432-881X |
Popis: | 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. |
Databáze: | OpenAIRE |
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