Superbases in Confined Space: Control of the Basicity and Reactivity of the Proton Transfer

详细信息    查看全文

• 作者：Bastien Chatelet ; Heinz Gornitzka ; V茅ronique Dufaud ; Erwann Jeanneau ; Jean-Pierre Dutasta ; Alexandre Martinez
• 刊名：Journal of the American Chemical Society
• 出版年：2013
• 出版时间：December 11, 2013
• 年：2013
• 卷：135
• 期：49
• 页码：18659-18664
• 全文大小：354K
• 年卷期：v.135,no.49(December 11, 2013)
• ISSN：1520-5126

文摘

Endohedral functionalization of the molecular cavity of host molecules is in high demand in many areas of supramolecular chemistry. When highly reactive species are incarcerated in the confined space of a molecular cavity, deep changes of their chemical properties are expected. Here, we show that the superbasic properties of proazaphosphatranes can be improved in the confined space of the molecular cavity of hemicryptophane hosts. A general and modular procedure is described to prepare supramolecular superbases with various cavity sizes. The rate of proton transfer is strongly dependent on the shape and size of the inner cavity of the designed superbasic structure. Kinetic and thermodynamic data are strongly correlated to the space available around the basic center as revealed by the X-ray molecular structures analyses.