Computational Study of Sulfur Atom-Transfer Reactions from Thiiranes to ER3 (E = As, P; R = CH3, Ph)

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• 作者：Abdellatif Ibdah ; James H. Espenson ; and William S. Jenks
• 刊名：Inorganic Chemistry
• 出版年：2005
• 出版时间：November 14, 2005
• 年：2005
• 卷：44
• 期：23
• 页码：8426 - 8432
• 全文大小：181K
• 年卷期：v.44,no.23(November 14, 2005)
• ISSN：1520-510X

文摘

Computational estimates have been made for the P=S and As=S bond strengths in triphenylphosphine sulfideand triphenylarsine sulfide, on the basis of G3 calculations for the methyl analogues and isodesmic-exchangereactions. Also, with the performance of the G3 method level for related compounds taken into consideration, thebest estimates are 82 and 68 kcal/mol, respectively. While the value for triphenylarsine sulfide is within 2 kcal/molof 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 Pand As, it is found that there is greater charge separation in the P=S bond. It is found that S atom transfer fromthiiranes to arsines is exothermic.