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Mechanism of thiolate-disulfide exchange: Addition-elimination or effectively S2? Effect of a shallow intermediate in gas-phase direct dynamics simulations

Journal of Physical Chemistry A, ISSN: 1089-5639, Vol: 116, Issue: 47, Page: 11492-11499
2012
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Direct dynamics trajectory simulations were performed for two examples of the thiolate-disulfide exchange reaction, that is, HS + HSSH and CHS + CHSSCH. 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 S2 pathway). Rather, the mechanism is addition-elimination, with several trajectories sampling the intermediate for long times, up to 15 ps or longer. © 2012 American Chemical Society.

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