Crossover Point between Dialkoxy Disulfides (ROSSOR) and Thionosulfites ((RO)2S=S): Prediction, Synthesis, and Structure

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• 作者：Eli Zysman-Colman ; Neysa Nevins ; Nicolas Eghbali ; James P. Snyder ; and David N. Harpp
• 刊名：Journal of the American Chemical Society
• 出版年：2006
• 出版时间：January 11, 2006
• 年：2006
• 卷：128
• 期：1
• 页码：291 - 304
• 全文大小：270K
• 年卷期：v.128,no.1(January 11, 2006)
• ISSN：1520-5126

文摘

Isomeric preference between cyclic dialkoxy disulfides and thionosulfites is governed by thering size of the heterocycle. Rings smaller than seven atoms prefer the thionosulfite connectivity, whereaslarger rings or acyclic analogues favor the unbranched dialkoxy disulfide structure. Density functionalcalculations were employed to predict the crossover point at which both constitutional isomers are ofcomparable stability. Follow-up synthesis provides the previously unknown eight-membered ring dialkoxydisulfide 14 and seven-membered ring thionosulfite 15 from the same reaction. X-ray crystallography forall but one of the reaction products and complementary NMR analysis furnishes insights into both solid-state and solution conformations. A long-standing issue regarding the concerted vs catalyzed isomerizationpathway between XSSX and X₂S=S has been addressed for X = RO and shown to be acid dependent.