Nitroxyl disulfides, novel intermediates in transnitrosation reactions.

Journal Article (Journal Article)

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.

Full Text

Duke Authors

Cited Authors

  • Houk, KN; Hietbrink, BN; Bartberger, MD; McCarren, PR; Choi, BY; Voyksner, RD; Stamler, JS; Toone, EJ

Published Date

  • June 2003

Published In

Volume / Issue

  • 125 / 23

Start / End Page

  • 6972 - 6976

PubMed ID

  • 12783550

Electronic International Standard Serial Number (EISSN)

  • 1520-5126

International Standard Serial Number (ISSN)

  • 0002-7863

Digital Object Identifier (DOI)

  • 10.1021/ja029655l


  • eng