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

Amber N. Hancock, Sofia Lobachevsky, Naomi L. Haworth, Michelle L. Coote, Carl H. Schiesser

Research output: Contribution to journalArticlepeer-review

4 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)2310-2316
Number of pages7
JournalOrganic and Biomolecular Chemistry
Volume13
Issue number8
DOIs
Publication statusPublished - 2015
Externally publishedYes

Bibliographical note

Publisher Copyright:
© The Royal Society of Chemistry 2015.

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