Bhattarai Sumitra, Sutradhar Dipankar, Chandra Asit K
Department of Chemistry, North Eastern Hill University, Shillong, 793022, India.
School of Advanced Sciences and Languages, VIT Bhopal University, Bhopal, 466114, Madhya Pradesh, India.
Chemphyschem. 2022 May 18;23(10):e202200146. doi: 10.1002/cphc.202200146. Epub 2022 Apr 26.
Ab initio calculation at the MP2/aug-cc-pVTZ level has been performed on the π-hole based N Si tetrel bonded complexes between substituted pyridines and H SiO. The primary aim of the study is to find out the effect of substitution on the strength and nature of this tetrel bond, and its similarity/difference with the N C tetrel bond. Correlation between the strength of the N Si bond and several molecular properties of the Lewis acid (H SiO) and base (pyridines) are explored. The properties of the tetrel bond are analyzed using AIM, NBO, and symmetry-adapted perturbation theory calculations. The complexes are characterized with short N Si intermolecular distances and high binding energies ranging between -142.72 and -115.37 kJ/mol. The high value of deformation energy indicates significant geometrical distortion of the monomer units. The AIM and NBO analysis reveal significant coordinate covalent bond character of the N⋅⋅⋅Si π-hole bond. Sharp differences are also noticed in the orbital interactions present in the N⋅⋅⋅Si and N⋅⋅⋅C tetrel bonds.
在MP2/aug-cc-pVTZ水平上对取代吡啶与H₂SiO之间基于π-空穴的N⋯Si四元键复合物进行了从头算计算。该研究的主要目的是找出取代基对这种四元键强度和性质的影响，以及它与N⋯C四元键的异同。探讨了N⋯Si键强度与路易斯酸（H₂SiO）和碱（吡啶）的几个分子性质之间的相关性。使用AIM、NBO和对称适配微扰理论计算分析了四元键的性质。这些复合物的特征是具有较短的N⋯Si分子间距离和介于-142.72至-115.37 kJ/mol之间的高结合能。变形能的高值表明单体单元存在显著的几何畸变。AIM和NBO分析揭示了N⋯Si π-空穴键具有显著的配位共价键特征。在N⋯Si和N⋯C四元键中的轨道相互作用也存在明显差异。
