Assessment of intermolecular interactions at three sites of the arylalkyne in phenylacetylene-containing lithium-bonded complexes: Ab initio and QTAIM studies

作者：Zeng Yanli^*; Zhu Min; Li Xiaoyan; Zheng Shijun; Meng Lingpeng

来源：Journal of Computational Chemistry, 2012, 33(14): 1321-1327.

DOI：10.1002/jcc.22962

• intermolecular interaction
• p-type lithium bond
• p electron density
• MFDD
• molecular electrostatic potentials

The intermolecular interactions existing at three different sites between phenylacetylene and LiX (X = OH, NH2, F, Cl, Br, CN, NC) have been investigated by means of second-order Muller-Plesset perturbation theory (MP2) calculations and quantum theory of atoms in molecules (QTAIM) studies. At each site, the lithium-bonding interactions with electron-withdrawing groups (?F, ?Cl, ?Br, ?CN, ?NC) were found to be stronger than those with electron-donating groups (?OH and ?NH2). Molecular graphs of C6H5C?CH...LiF and pC6H5C?CH...LiF show the same connectional positions, and the electron densities at the lithium bond critical points (BCPs) of the pC6H5C?CH...LiF complexes are distinctly higher than those of the sC6H5C?CH...LiF complexes, indicating that the intermolecular interactions in the C6H5C?CH...LiX complexes can be mainly attributed to the p-type interaction. QTAIM studies have shown that these lithium-bond interactions display the characteristics of closed-shell noncovalent interactions, and the molecular formation density difference indicates that electron transfer plays an important role in the formation of the lithium bond. For each site, linear relationships have been found between the topological properties at the BCP (the electron density ?b, its Laplacian ?2?b, and the eigenvalue ?3 of the Hessian matrix) and the lithium bond length d(Li-bond). The shorter the lithium bond length d(Li-bond), the larger ?b, and the stronger the p...Li bond. The shorter d(Li-bond), the larger ?2?b, and the greater the electrostatic character of the p...Li bond.

• 出版日期2012-5-30
• 单位河北师范大学