title: First-principles prediction of rate coefficients for free-radical cyclization reactions at selenium.
abstract: High-level ab initio calculations of the barriers, enthalpies, and rate coefficients for the intramolecular cyclization reactions of *CH(2)CH(2)CH(2)CH(2)SeR (R = Me, n-Bu, s-Bu, t-Bu, Bn, Bz, Ph(2)CH) and *CH(2)CH(2)CH(2)CH(2)CHCH(2) 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 10(4)-10(6) 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.
authors.affiliation: ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, University of Melbourne, Victoria, 3010 Australia.
authors.forename: Sofia
authors.initials: S
authors.lastname: Lobachevsky
authors.forename: Carl H
authors.initials: CH
authors.lastname: Schiesser
authors.forename: Ching Yeh
authors.initials: CY
authors.lastname: Lin
authors.forename: Michelle L
authors.initials: ML
authors.lastname: Coote
mesh_terms: D000465:Algorithms; D003500:Cyclization; D005609:Free Radicals / Q000737:chemistry*; D007700:Kinetics; D008956:Models, Chemical; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory; D012643:Selenium / Q000737:chemistry*; D055672:Static Electricity; D013816:Thermodynamics
chemical_list: D005609:Free Radicals; D009942:Organometallic Compounds; D012643:Selenium