Author： Rudakov E. S.
Publisher： Springer Publishing Company
ISSN： 0040-5760
Source： Theoretical and Experimental Chemistry, Vol.39, Iss.5, 2003-01, pp. : 296-302
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Abstract
We have determined the differences in the parameters Δlog A and ΔE of the Arrhenius equations for the kinetic isotope effect (KIE) (c-C6H12/c-C6D12) and the 5/6 effect (c-C5H10/c-C6H12) in reactions of the C—H bonds of cycloalkanes with adamantyl (Ad+) carbocations (1-adamantanol in 92.8% H2SO4, 40-97 °C). We have established the compensation relations between Δlog A and ΔE for the kinetic isotope effect and the 5/6 effect for anthracene (AH+), hydroxymethyl (CH2OH+), Ad+ carbocations and the hypothetical "infinitely strong reagent," supporting a hydride transfer mechanism in such reactions.
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