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Digitale Medien

Deuterium isotope cage effects in the dismutation of alkoxyl radicals. Significance for the mode of alkylperoxyl termination (1985)

Mendenhall, G. D. ; Quinga, E. M. Y.

New York, NY : Wiley-Blackwell

International Journal of Chemical Kinetics 17 (1985), S. 1187-1190

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Details

ISSN: 0538-8066

Schlagwort(e): Chemistry ; Physical Chemistry

Quelle: Wiley InterScience Backfile Collection 1832-2000

Thema: Chemie und Pharmazie

Notizen: 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.

Zusätzliches Material: 1 Tab.

Materialart: Digitale Medien

URL: http://dx.doi.org/10.1002/kin.550171104

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