Publications [#234200] of Eric J. Toone

Journal Articles

1. Houk, KN; Hietbrink, BN; Bartberger, MD; McCarren, PR; Choi, BY; Voyksner, RD; Stamler, JS; Toone, EJ, Nitroxyl disulfides, novel intermediates in transnitrosation reactions., Journal of the American Chemical Society, vol. 125 no. 23 (June, 2003), pp. 6972-6976, ISSN 0002-7863 [12783550], [doi]
   (last updated on 2026/01/13)

   Abstract:
   A novel anionic RSN(O)SR species, the intermediate in transnitrosation reactions, was explored computationally with B3LYP and CBS-QB3 methods. The species resembles a nitroxyl coordinated to a highly distorted disulfide, and it differs significantly from intermediates in nucleophilic acyl substitution. Reactions of the following species were computed for comparison: MeS(-) + MeSNO; MeO(-) + MeONO; MeS(-) + MeSCHO; MeO(-) + MeOCHO. The last two have very different intermediates from the first two. Mass spectrometric experimental evidence is presented that is consistent with the formation of a nitroxyl disulfide in the gas phase. The calculated proton affinity and redox potentials of the intermediate are also reported.