Three-electron σ-bonded radicals: an electron paramagnetic resonance spectroscopic study of R3P—Cl radicals in freon
- 1 January 1990
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Faraday Transactions
- Vol. 86 (19) , 3293-3298
- https://doi.org/10.1039/ft9908603293
Abstract
Our main purpose is to draw attention to the relative stability of three-electron σ-bonded radicals (σ2 1, σ1 2), the large number of such radicals that have been studied by EPR spectroscopists, and their potential importance as reaction intermediates. The topic is illustrated by experiments which show that when R3P˙+ radical cations (Me3P˙+ and Ph3P˙+) are generated in CFCl3 at 77 K by exposure to 60Co γ-rays, and the system is annealed to ca. 155 K, features characteristic of R3P[graphic omitted]Cl radicals are detected, with well defined hyperfine coupling to 31P and 35/37Cl nuclei. It is argued that these must have been formed from chloride ions released from (CFCl3)˙– radical-anions following electron capture.Keywords
This publication has 39 references indexed in Scilit:
- Evidence of three-electron covalent bond firmsChemical & Engineering News, 1987
- Pyridine complexes of chlorine atomsJournal of the American Chemical Society, 1987
- Selective steroid chlorinations directed by attached pyridine ester templatesJournal of the American Chemical Society, 1987
- Chlorine atom/benzene system. 1. The role of 6-chlorocyclohexadienyl radicalJournal of the American Chemical Society, 1986
- π Complexing of chlorine atoms: is that all there is?Journal of the American Chemical Society, 1983
- Electron-loss and electron-capture processes in irradiated systemsPure and Applied Chemistry, 1981
- Stabilization of oxidized sulfur centers in organic sulfides. Radical cations and odd-electron sulfur-sulfur bondsAccounts of Chemical Research, 1979
- Unstable intermediates. Part CLIX. Dihalide anions and related species as products in the radiolysis of organic halidesJournal of the Chemical Society, Perkin Transactions 2, 1975
- Formation of positive ions in the reaction of disulfides with hydroxyl radicals in aqueous solutionThe Journal of Physical Chemistry, 1974
- Electron spin resonance spectra and structures of some σ* radicalsJournal of the Chemical Society, Chemical Communications, 1972