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

Document Type

Article

Publication Date

1-1-1985

Department

Department of Chemistry; Department of Chemical Engineering

Abstract

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.

Publisher's Statement

Copyright © 1985 John Wiley & Sons, Inc. Publisher’s version of record: https://doi.org/10.1002/kin.550171104

Publication Title

International Journal of Chemical Kinetics

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