The electron-spin resonance spectra of the electrolytically generated radical-anions of the nitrothiophens
- 1 January 1966
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc. A
- p. 991-994
- https://doi.org/10.1039/j19660000991
Abstract
The radical-anions of 2-nitro-, 3-nitro-, and 2,5-dinitro-thiophen have been generated by electrolysis of their solutions in both acetonitrile and dimethylformamide, and their electron-spin resonance spectra measured. The proton hyperfine splitting constants have been assigned by observation of the spectra of various methylated derivatives. Spin-densities have been calculated by McLachlan's extension of the Hückel molecular orbital method, using models for the sulphur atom in which either only the occupied 3pz orbital interacts with the π-system (p-model) or where the vacant 3d orbitals are also taken into account (d-model). Both models give fairly adequate predictions of the experimental results. A suitable set of parameters to describe the sulphur atom in the p-model for both these compounds and the radical-anions of dibenzothiophen and its derivatives is αS=α+ 1·0β, βCS= 0·7β, where α and β have their usual significance.Keywords
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