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• W1557896500 abstract "It is shown that solvent holes in cis- and trans-decalin form complexes with aliphatic alcohols that live 1−100 ns, depending on the solute and the solvent temperature. This complexation has near-zero activation energy and occurs with rate constants of (1−1.2) × 1011 M-1 s-1 in trans-decalin and 3 × 1010 M-1 s-1 in cis-decalin. The metastable complex decays by proton transfer (for alcohols higher than ethanol); in concentrated solutions a diffusion-controlled reaction of the complex with a second alcohol molecule occurs. While the stability of the complex increases with the carbon number of the alcohol, the standard heat of the complexation decreases in the opposite direction (ΔH° changes from −39 kJ/mol for ethanol to −25 kJ/mol for tert-butanol). The decrease in the standard entropy is small (Δ > −80 J mol-1 K-1), approaching zero for higher alcohols. We argue that this thermochemistry is due to the polaronic nature of the solvent holes." @default.
• W1557896500 created "2016-06-24" @default.
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• W1557896500 date "2000-04-01" @default.
• W1557896500 modified "2023-09-27" @default.
• W1557896500 title "Reversible Reactions of Cycloalkane Solvent Holes. 1. Complexation ofcis-andtrans-Decalin•+with Alcohols" @default.
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• W1557896500 doi "https://doi.org/10.1021/jp993988w" @default.
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