Deuterium isotope cage effects in the dismutation of alkoxyl radicals. Significance for the mode of alkylperoxyl termination

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Decomposition of (R1R2CXON=)2 (R1 = R2 = Ph; R1 = R2 = pClC6H4; R1 = Ph, R2 = CH3; X = H or D) in hydrocarbon solvents at 31–75°C afforded R1R2CO in 6–8% 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 α‐deuteration. Copyright © 1985 John Wiley & Sons, Inc.

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International Journal of Chemical Kinetics