Esrafili Mehdi D, Asadollahi Soheila
Laboratory of Theoretical Chemistry, Department of Chemistry, University of Maragheh, Maragheh, Iran.
Laboratory of Theoretical Chemistry, Department of Chemistry, University of Maragheh, Maragheh, Iran.
J Mol Graph Model. 2017 May;73:200-207. doi: 10.1016/j.jmgm.2017.01.005. Epub 2017 Mar 2.
In this work, we investigate the effect of a cation-π interaction on the cooperativity of X⋯N halogen bonds in PhX⋯NCX⋯NH complexes, where Ph=phenyl and X=Cl, Br, I. Molecular geometries and interaction energies of the resulting complexes are studied at the MP2/aug-cc-pVDZ(-PP) computational level. The mechanism of the cooperativity between halogen bonds is analyzed using parameters derived from the noncovalent index, quantum theory of atoms in molecules and natural bond orbital methodologies. It is found that the divalent cations (Be, Mg) have a larger influence on the cooperativity of halogen bonds than monovalent ones (Li, Na). The formation of a cation-π interaction leads to strengthening of the halogen bonds, hence increases their cooperativity.
在本研究中，我们研究了阳离子-π相互作用对PhX⋯NCX⋯NH络合物中X⋯N卤键协同性的影响，其中Ph = 苯基，X = Cl、Br、I。在MP2/aug-cc-pVDZ(-PP)计算水平上研究了所得络合物的分子几何结构和相互作用能。使用从非共价指数、分子中的原子量子理论和自然键轨道方法导出的参数分析了卤键之间协同性的机制。发现二价阳离子（Be、Mg）对卤键协同性的影响比一价阳离子（Li、Na）更大。阳离子-π相互作用的形成导致卤键增强，从而增加了它们的协同性。
