Electron spin resonance studies of the photolysis and radiolysis of O,O′-dialkyl hydrogen phosphorodithioates [(RO)<sub>2</sub>P(S)SH], their salts, corresponding disulphides, and related compounds: formation of thio and dithio radicals, radical ions, and phosphorus-centred radicals

Gilbert, Bruce C.; Kelsall, Paul A.; Sexton, Michael D.; Mcconnacchie, G. D. G.; Symons, Martyn C. R.

doi:10.1039/p29840000629

Cited by 34 publications

(10 citation statements)

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“…The values of P3p/P3s are close to 2 (except for radical c in [(MeO)2P(S)S]zCd ) and the isotropic hyperfine splitting (Aiso) is 800-900 G, which are typical parameters for phosphoranyl radicals [8]. Similar results have been reported previously for EPR study of powdered [(PriO)2P(S)S]2Zn [3].…”

Section: Phosphorus-centered Radicalssupporting

confidence: 75%

“…For many years the formation and structure of free radicals, produced by ionizing radiation have received much attention and among them phosphorus-centered radicals are of continuous interest [1][2][3]. The studies have established that the configuration of the radical, formed asa result of the irradiation, strongly depends on the nature of the substituents bonded to the phosphorus atom [1][2][3].…”

Section: Introductionmentioning

confidence: 99%

“…The studies have established that the configuration of the radical, formed asa result of the irradiation, strongly depends on the nature of the substituents bonded to the phosphorus atom [1][2][3].…”

Section: Introductionmentioning

confidence: 99%

“…It was established [3] that the exposure of some salts of dithiophosphoric acid to gamma or X-ray irradiation at 77 K results in the formation of three types of free radicals: (1) alkyl radicals formed by splitting a C-O bond in an electron addition reaction; (2) free radicals derived by hydrogen atom abstraction, usually from the carbon adjacent to the oxygen, through ionic intermediates, and (3) phosphorus-centered radicals generated by cleavage of a phosphorus-oxygen or phosphorus-sulfur bond. The proposed mechanism for the formation of the last species is dissociative electron capture to give phosphoryl radicals [3].…”

Section: Introductionmentioning

confidence: 99%

“…The proposed mechanism for the formation of the last species is dissociative electron capture to give phosphoryl radicals [3]. The electron gain process giving phosphoranyl radicals is also considered in the reactions of dithiophosphate salts on radiolysis.…”

Section: Introductionmentioning

confidence: 99%

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EPR studies of X-ray irradiated dithiophosphate metal complexes

Zdravkova

Hüttermann

1997

Appl. Magn. Reson.

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Abstraet. Different metal O,O'-disubstituted dithiophosphates have been studied by Electron Paramagnetic Resonance (EPR) spectroscopy after X-ray irradiation at 77 K. Formation of different radicals has been recorded depending on the central metal atom and on the substituents in the ligands. Phosphorus-centered radicals with hyperfine constants of about 800 G were recorded after radiolysis of zinc and cadmium complexes. Their shape and EPR parameters lead to their identification as phosphoranyl radicals (RO)2P'(S)S-. In these compounds two different types of coordination of the ligands have been found by X-ray analysis. One dithiophosphate group is coordinated to the metal atom forming a chelate four-membered ring, and another one is a bridging group. The formation of phosphorus-centered radicals is related to the presente of a bridging, or interchelating group. In other metal dithiophosphates, with only chelating groups present, such radicals were not found. In platinum, palladium and nickel dithiophosphates similar EPR signals with small hyperfine coupling were observed. They have been identified as carbon-centered radicals with one phosphorus in y-position.

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Section: Phosphorus-centered Radicalssupporting

confidence: 75%