The Role of Nonbonded Sulfur−Oxygen Interaction in the Dissociative Electron Transfer to Nitro-Substituted Arenesulfenyl Chlorides
- 15 June 2004
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (26), 8076-8077
- https://doi.org/10.1021/ja049575c
Abstract
The electrochemical reduction of p-nitrophenyl sulfenyl chloride, o-nitrophenyl sulfenyl chloride as well as bis(4-nitrophenyl) disulfide and bis(2-dinitrophenyl) disulfide was investigated in acetonitrile at an inert electrode. Reduction standard potentials as well standard heterogeneous electron-transfer rate constants have been determined using convolution analysis. An unexpected big difference in the thermodynamics and kinetics of the initial electron-transfer process as well as a striking change in the reductive cleavage mechanism of the S−Cl bond as a function of the nitro group position on the aryl ring of the aryl sulfenyl chloride is observed. A computational study at the B3LYP level shows that this difference in behavior is due to the through-space nonbonded S···O interaction in the o-nitrophenyl sulfenyl chloride.This publication has 25 references indexed in Scilit:
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