Nitroxyl disulfides, novel intermediates in transnitrosation reactions.
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.
Houk
K N
KN
Department of Chemistry and Biochemistry, University of California, Los Angeles, 405 Hilgard Avenue, Los Angeles, California 90095-1569, USA. houk@chem.ucla.edu
Hietbrink
Bruce N
BN
Bartberger
Michael D
MD
McCarren
Patrick R
PR
Choi
Bo Yoon
BY
Voyksner
Robert D
RD
Stamler
Jonathan S
JS
Toone
Eric J
EJ
D004220:Disulfides / Q000737:chemistry*; D008958:Models, Molecular; D009589:Nitrogen Oxides / Q000737:chemistry*; D015538:Nitrosation; D009603:Nitroso Compounds / Q000737:chemistry; D013438:Sulfhydryl Compounds / Q000737:chemistry; D013816:Thermodynamics
D004220:Disulfides; D009589:Nitrogen Oxides; D009603:Nitroso Compounds; D013438:Sulfhydryl Compounds; C039900:nitroxyl