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Temperature Dependence of the Ratios of C—H (C—D) Bond Breaking Rates in Reactions of Cycloalkanes C5H10, C6H12, C6D12 with Adamantyl Carbocations in Sulfuric Acid

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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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Authors and Affiliations

  1. L. M. Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine, 70 R. Luxemburg Vul., 83114, Donets'k, Ukraine

    E. S. Rudakov & L. K. Volkova

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  1. E. S. Rudakov
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  2. L. K. Volkova
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Rudakov, E.S., Volkova, L.K. Temperature Dependence of the Ratios of C—H (C—D) Bond Breaking Rates in Reactions of Cycloalkanes C5H10, C6H12, C6D12 with Adamantyl Carbocations in Sulfuric Acid. Theoretical and Experimental Chemistry 39, 296–302 (2003). https://doi.org/10.1023/B:THEC.0000003490.64710.c1

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