Asymmetry and non-adiabaticity in fragmentation of disulfide bonds upon electron capture

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry
José A GámezManuel Yáñez

Abstract

Although it has been generally assumed that electron attachment to disulfide derivatives leads to a systematic and significant activation of the S-S bond, we show, by using [CH(3)SSX] (X = CH(3), NH(2), OH, F) derivatives as model compounds, that this is the case only when the X substituents have low electronegativity. Through the use of MP2, QCI and CASPT2 molecular orbital (MO) methods, we elucidate, for the first time, the mechanisms that lead to unimolecular fragmentation of disulfide derivatives after electron attachment. Our theoretical scrutiny indicates that these mechanisms are more intricate than assumed in previous studies. The most stable products, from a thermodynamic viewpoint, correspond to the release of neutral molecules; CH(4), NH(3), H(2)O, and HF. However, the barriers to reach these products depend strongly on the electronegativity of the X substituents. Only for very electronegative substituents, such as OH or F, the loss of H(2)O or HF is the most favorable process, and likely the only one observed. This is possible because of two concomitant factors, 1) the extra electron for [CH(3)SSX](-) (X = OH, F) occupies a sigma*(S-X) MO, which favors the cleavage of the S-X bond, and 2) the activation barriers ass...Continue Reading

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Jan 23, 2010·Physical Chemistry Chemical Physics : PCCP·José A GámezManuel Yáñez

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Citations

Feb 26, 2011·Chemical Communications : Chem Comm·José A Gámez, Manuel Yáñez
Mar 23, 2012·The Journal of Physical Chemistry. a·Robert F HöckendorfMartin K Beyer
Sep 17, 2013·Journal of Computational Chemistry·Otilia MóRussell J Boyd
Jan 31, 2013·Chemistry : a European Journal·Gavin S Heverly-CoulsonManuel Yáñez
Feb 22, 2013·Chemistry : a European Journal·Goedele RoosPaul Geerlings
Nov 22, 2013·Journal of Biomolecular Structure & Dynamics·Goedele RoosF Matthias Bickelhaupt
Jun 14, 2011·Journal of Chemical Theory and Computation·José A Gámez, Manuel Yáñez

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