Aerogen bonds formed between AeOF2 (Ae = Kr, Xe) and diazines: comparisons between σ-hole and π-hole complexes†,Physical Chemistry Chemical Physics

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Aerogen bonds formed between AeOF2 (Ae = Kr, Xe) and diazines: comparisons between σ-hole and π-hole complexes†
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2018-01-10 00:00:00 , DOI: 10.1039/c7cp08048d
Wiktor Zierkiewicz _{1,

2,

3,

4} , Mariusz Michalczyk _{1,

2,

3,

4} , Steve Scheiner _{5,

6,

7,

8}

Affiliation

The interaction between KrOF₂ or XeOF₂ and the 1,2, 1,3, and 1,4 diazines is characterized chiefly by a Kr/Xe⋯N aerogen bond, as deduced from ab initio calculations. The most stable dimers take advantage of the σ-hole on the aerogen atom, wherein the two molecules lie in the same plane. The interaction is quite strong, as much as 18 kcal mol⁻¹. A second class of dimer geometry utilizes the π-hole above the aerogen atom in an approximate perpendicular arrangement of the two monomers; these structures are not as strongly bound: 6–8 kcal mol⁻¹. Both sorts of dimers contain auxiliary CH⋯F H-bonds which contribute to their stability, but even with their removal, the aerogen bond energy remains as high as 14 kcal mol⁻¹. The nature and strength of each specific interaction is confirmed and quantified by AIM, NCI, NBO, and electron density shift patterns. There is not a great deal of sensitivity to the identity of either the aerogen atom or the position of the two N atoms in the diazine.

中文翻译：

AeOF ₂（Ae = Kr，Xe）与二嗪之间形成的气键：σ-孔和π-孔配合物的比较†

KrOF之间的相互作用₂或XeOF ₂和1,2-，1,3-和1,4-二嗪是由氪/氙⋯Ñ键的Aerogen主要特征，如从推导出从头计算。最稳定的二聚体利用了气源原子上的σ孔，其中两个分子位于同一平面上。相互作用非常强，高达18 kcal mol ^-1。第二类二聚体几何结构是利用气孔原子上方的π孔以两种单体近似垂直的方式排列的。这些结构没有那么牢固的结合：6–8 kcal mol ^-1。两种类型的二聚体均包含有助于其稳定性的辅助CH⋯F H键，但即使将其除去，气原键能仍保持高达14 kcal mol ^-1。每种特定相互作用的性质和强度均通过AIM，NCI，NBO和电子密度转换模式进行了确认和量化。对气源原子的身份或二嗪中两个N原子的位置没有很大的敏感性。

更新日期：2018-01-10

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