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Structure and stability of 2σ/1σ* three‐electron‐bonded radical cations from 1, n ‐bis(alkylthio)alkanes in aqueous solutions
Author(s) -
Anklam Elke,
Asmus KlausDieter,
Mohan Hari
Publication year - 1990
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610030105
Subject(s) - chemistry , intramolecular force , intermolecular force , aqueous solution , radiolysis , radical , sulfur , electron density , crystallography , electron , medicinal chemistry , photochemistry , molecule , stereochemistry , organic chemistry , physics , quantum mechanics
A large number of 1, n ‐bis(alkylthio)alkanes, R′S(CH 2 ) n SR″, was investigated by pulse radiolysis in aqueous solutions. The sulphur‐centred radical cations, which were obtained on oxidation of the dithia compounds by ·OH radicals, are stabilized via 2σ/1σ* three‐electron interaction between two sulphur atoms. Intramolecular stabilization is the only process observed for n = 2–4, whereas for longer chain compounds with n > 4 some intermolecular sulphur–sulphur interaction is also indicated. The stability and yields of the three‐electron‐bonded species also depend on the nature of the substituents R′ and R″, and for the intermolecular systems are a function of solute concentration. The results corroborate earlier investigations and demonstrate, in particular, that the optical parameters are a very sensitive measure of changes in electron density and structure of the three‐electron‐bonded systems.