Computational Study of Sulfur Atom-Transfer Reactions from Thiiranes to ER3 (E = As, P; R = CH3, Ph)Inorganic Chemistry
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AbstractComputational estimates have been made for the PS and AsS bond strengths in triphenylphosphine sulfide and triphenylarsine sulfide, on the basis of G3 calculations for the methyl analogues and isodesmic-exchange reactions. Also, with the performance of the G3 method level for related compounds taken into consideration, the best estimates are 82 and 68 kcal/mol, respectively. While the value for triphenylarsine sulfide is within 2 kcal/mol of the single experimental estimate, that for triphenylphosphine sulfide is lower by 6 kcal/mol. (Capps, K. B.; Wixmerten, B.; Bauer, A.; Hoff, C. D. Inorg. Chem. 1998, 37, 2861−2864.) Despite virtually identical electronegativities of P and As, it is found that there is greater charge separation in the PS bond. It is found that S atom transfer from thiiranes to arsines is exothermic.
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Copyright OwnerAmerican Chemical Society
Citation InformationAbdellatif Ibdah, James H. Espenson and William S. Jenks. "Computational Study of Sulfur Atom-Transfer Reactions from Thiiranes to ER3 (E = As, P; R = CH3, Ph)" Inorganic Chemistry Vol. 44 Iss. 23 (2005) p. 8426 - 8432
Available at: http://works.bepress.com/william_jenks/14/