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Mechanism of thiolate-disulfide exchange: addition-elimination or effectively S(N)2? Effect of a shallow intermediate in gas-phase direct dynamics simulations.

Authors
  • Paranjothy, Manikandan
  • Siebert, Matthew R
  • Hase, William L
  • Bachrach, Steven M
Type
Published Article
Journal
The Journal of Physical Chemistry A
Publisher
American Chemical Society
Publication Date
Nov 29, 2012
Volume
116
Issue
47
Pages
11492–11499
Identifiers
DOI: 10.1021/jp307795j
PMID: 23116226
Source
Medline
License
Unknown

Abstract

Direct dynamics trajectory simulations were performed for two examples of the thiolate-disulfide exchange reaction, that is, HS(-) + HSSH and CH(3)S(-) + CH(3)SSCH(3). The trajectories were computed for the PBE0/6-31+G(d) potential energy surface using both classical microcanonical sampling at the ion-dipole complex and quasi-classical Boltzmann sampling (T = 300 K) at the central transition state. The potential energy surface for these reactions involves a hypercoordinate sulfur intermediate. Despite the fact that the intermediate resides in a shallow well (less than 5 kcal/mol), very few trajectories follow a direct substitution path (the S(N)2 pathway). Rather, the mechanism is addition-elimination, with several trajectories sampling the intermediate for long times, up to 15 ps or longer.

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