First-Principles Prediction of Rate Coefficients for Free-Radical Cyclization Reactions at Selenium

Sofia Lobachevsky, Carl H. Sehiesser, Ching Yeh Lin, Michelle L. Coote

Research output: Contribution to journalArticlepeer-review

22 Citations (Scopus)


High-level ab initio calculations of the barriers, enthalpies, and rate coefficients for the intramolecular cyclization reactions of ·CH 2CH2CH2CH2SeR (R = Me, w-Bu, s-Bu, t-Bu, Bn, Bz, Ph2CH) and ·CH2CH2CH 2CH2CH=CH2 have been performed at the G3(MP2)-RAD level. The calculated rate coefficients show excellent agreement with experiment (to within a factor of 5 or better), although this might be due, in part, to a systematic cancelation of order-of-magnitude errors in the corresponding Arrhenius parameters. The intramolecular cyclizations at selenium were found to be energetically favorable processes that occur with synthetically accessible rate coefficients on the order of 104-106 s-1 at 294 K. These values are largely governed by the stabilization energy of the leaving radical, though with contributions from steric and polar effects.

Original languageEnglish
Pages (from-to)13622-13627
Number of pages6
JournalJournal of Physical Chemistry A
Issue number51
Publication statusPublished - 25 Dec 2008
Externally publishedYes


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