Thiophosphonyl Radicals Photolytic Generation and Reactivity Towards Olefinic Compounds
Open Access
- 1 June 1985
- journal article
- research article
- Published by Walter de Gruyter GmbH in Zeitschrift für Naturforschung A
- Vol. 40 (6) , 541-543
- https://doi.org/10.1515/zna-1985-0601
Abstract
Upon irradiation with UV light (λ = 347 nm), 2,4,6-trimethylbenzoyldiphenylphosphine sulfide was found to be fragmented into free radicals by α-scission (F(k) = 0.3 ± 0.1): Flash photolysis studies revealed that the optical absorption spectrum of diphenylthiophosphonyl radicals, S = P(Ph)2. possesses a strong band with λmax = 340 nm and a somewhat weaker band with λmax ≈ 500 nm (e340nm = 1.2 ± 0.2) · 104 1/mol cm). The reactivity towards olefinic compounds, M, is 10 to 30 times lower than in the case of O = P(Ph)2 radicals. Typical bimolecular rate constants (in 1/mol s) of the reaction of S = P(Ph)2 with M are: 4 x 106 (styrene), 6.2 x 105 (methylacrylate), 4.2 x 104 (vinyl acetate).Keywords
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