✦ LIBER ✦
Deuterium isotope cage effects in the dismutation of alkoxyl radicals. Significance for the mode of alkylperoxyl termination
✍ Scribed by G. D. Mendenhall; E. M. Y. Quinga
- Publisher
- John Wiley and Sons
- Year
- 1985
- Tongue
- English
- Weight
- 174 KB
- Volume
- 17
- Category
- Article
- ISSN
- 0538-8066
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✦ Synopsis
Decomposition of (RIRzCXON=)2 (RI = R2 = Ph; R, = Rz = p-ClC6H,; Rl = Ph, Rz = CH3; X = H or D) in hydrocarbon solvents at 31-75°C afforded R,R$O in 64% lower yield when X = D than when X = H. This result is ascribed to cage escape of secondary alkoxyl radicals in competition with dismutation. Deuterium isotope effects for alkoxyl cage dismutation of 1.35-2.4 are estimated from the data. It is suggested that this same competition may account for the experimentally slower termination rate constants in solution of primary and secondary alkylperoxyl radicals on a-deuteration.