Computational Study of Sulfur Atom-Transfer Reactions from Thiiranes to ER3 (E = As, P; R = CH3, Ph)
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The Department of Chemistry seeks to provide students with a foundation in the fundamentals and application of chemical theories and processes of the lab. Thus prepared they me pursue careers as teachers, industry supervisors, or research chemists in a variety of domains (governmental, academic, etc).
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The Department of Chemistry was founded in 1880.
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1880-present
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- College of Liberal Arts and Sciences (parent college)
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Abstract
Computational 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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Reprinted (adapted) with permission from Inorganic Chemistry, 44(23); 8426-8432. Doi: 10.1021/ic051228w. Copyright 2005 American Chemical Society.