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Issue 8, 2015
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The effect of leaving radical on the formation of tetrahydroselenophene by SHi ring closure: an experimental and computational study

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Abstract

Competition kinetic studies augmented with laser-flash photolysis and high-level computational techniques [G3(MP2)-RAD], with [COSMO-RS, SMD] and without solvent correction, provide kinetic parameters for the ring closures of a series of 4-(alkylseleno)butyl radicals 1. At 22 °C rate constants (kc) that lie between 104–107 s−1 were determined experimentally and correlate with expectations based on leaving group ability. Activation energies (Eact) were determined to lie between 10.6 (R = Ph2CH) and 28.0 (R = n-Bu) kJ mol−1, while log(A/s−1) values were generally between 9 and 10 in benzene. Computationally determined rate constants were in good-to-excellent agreement with those determined experimentally, with the COSMO-RS solvation model providing values that more closely resemble those from experiment than SMD.

Graphical abstract: The effect of leaving radical on the formation of tetrahydroselenophene by SHi ring closure: an experimental and computational study

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The article was received on 19 Nov 2014, accepted on 16 Dec 2014 and first published on 02 Jan 2015


Article type: Paper
DOI: 10.1039/C4OB02434F
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Org. Biomol. Chem., 2015,13, 2310-2316

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    The effect of leaving radical on the formation of tetrahydroselenophene by SHi ring closure: an experimental and computational study

    A. N. Hancock, S. Lobachevsky, N. L. Haworth, M. L. Coote and C. H. Schiesser, Org. Biomol. Chem., 2015, 13, 2310
    DOI: 10.1039/C4OB02434F

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