Cooperativity between hydrogen- and halogen bonds: the case of selenourea†,Physical Chemistry Chemical Physics

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Cooperativity between hydrogen- and halogen bonds: the case of selenourea†
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2018-02-26 00:00:00 , DOI: 10.1039/c8cp00353j
Gianluca Ciancaleoni _{1,

2,

3,

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Affiliation

A combined experimental/computational study of cooperativity between halogen-(XB) and hydrogen bonding (HB) is presented. Selenourea (SeU) has been chosen due to its ability to act at the same time as an XB acceptor toward I(CF₂)₅CF₃ (I1) through the two lone pairs on the selenium atom, and as a HB donor to the benzoate anion through its two amino moieties. All equilibrium constants have been estimated using either diffusion NMR and NMR titration techniques. Experimental results demonstrate that the –NH₂⋯anion interaction strongly enhances the Se⋯I one of about one order of magnitude (in terms of formation constant of the adduct), whereas DFT results rationalize such results revealing that the presence of a HB between the benzoate and SeU strongly polarizes the latter, enhancing the negative partial charge on selenium and, consequently, its Lewis basicity and its XB acceptor properties.

中文翻译：

氢键和卤素键之间的协同作用：硒硒†

提出了结合实验/计算研究的卤素-（XB）和氢键（HB）之间的协同作用。之所以选择Selenourea（SeU），是因为它具有与XB受体同时通过硒原子上的两个孤对作用于I（CF ₂）₅ CF ₃（I1）的能力，以及作为XB受体的HB供体。通过其两个氨基部分形成苯甲酸酯阴离子。使用扩散NMR和NMR滴定技术都可以估算所有平衡常数。实验结果表明，–NH ₂阴离子相互作用强烈地增强了Se⋯I约一个数量级（就加合物的形成常数而言），而DFT结果使这些结果合理化，表明苯甲酸盐和SeU之间存在HB强烈极化了后者。增强硒的负部分电荷，从而增强其Lewis碱性和XB受体性能。

更新日期：2018-02-26

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