Halide ion capture by radicals. Electron spin resonance spectra of R3P·—hal and R2S·—hal σ*radicals
- 1 January 1979
- journal article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics
- Vol. 75, 210-219
- https://doi.org/10.1039/f29797500210
Abstract
Exposure of methanolic or acidic aqueous glasses containing halide salts together with organic phosphines or sulphides gave the electron loss centres R3P˙+ or R2S˙+ which reacted with halide ions (hal–) to give the σ* radicals R3P·—hal and R2S·—hal which were identified by e.s.r. spectroscopy. These were formed in competition with the σ* dimer radicals R3P·—PR3 + and R2S·—SR2 +, also detected by e.s.r. spectroscopy. Interconversion between these species on annealing the glasses above 77 K is discussed. These reactions are significant in being the reverse of dissociative electron capture. Also, they constitute a method of converting an electron-loss centre into an electron excess centre.Keywords
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