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Kinetics and mechanism of monomolecular heterolysis of commercial organohalogen compounds: XXXVIII. Correlation analysis of solvent effects on the activation parameters of heterolysis of t-BuBr and t-BuI

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Abstract

Heterolysis of t-BuBr and t-BuI in aprotic solvents involves a ΔH ≠-Δ S ≠ compensation effect. The ΔG ≠ of t-BuBr heterolysis in aprotic solvents decreases with increasing solvent polarity and cohesion, whereas the respective value for t-BuI heterolysis decreases with increasing solvent polarity, nucleophilicity, and polarizability. In protic solvents, a negative effect of nucleophilic solvation is observed.

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Authors and Affiliations

  1. Kiev Polytechnic Institute, National Technical University of Ukraine, Kiev, Ukraine

    N. E. Ponomarev, V. V. Zaliznyi & G. F. Dvorko

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  1. N. E. Ponomarev
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  2. V. V. Zaliznyi
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  3. G. F. Dvorko
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Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 9, 2004, pp. 1476–1483.

Original Russian Text Copyright © 2004 by Ponomarev, Zaliznyi, Dvorko.

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Ponomarev, N.E., Zaliznyi, V.V. & Dvorko, G.F. Kinetics and mechanism of monomolecular heterolysis of commercial organohalogen compounds: XXXVIII. Correlation analysis of solvent effects on the activation parameters of heterolysis of t-BuBr and t-BuI. Russ J Gen Chem 74, 1368–1375 (2004). https://doi.org/10.1007/s11176-005-0013-8

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  • DOI: https://doi.org/10.1007/s11176-005-0013-8

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