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Comparison of σ‐/π‐Hole Tetrel Bonds between TH 3 F/F 2 TO and H 2 CX (X=O, S, Se)
Author(s) -
Dong Wenbo,
Niu Bingbo,
Liu Shufeng,
Cheng Jianbo,
Liu Shaoli,
Li Qingzhong
Publication year - 2019
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201800990
Subject(s) - crystallography , atom (system on chip) , chalcogen , covalent bond , binding energy , polarization (electrochemistry) , interaction energy , chemistry , materials science , atomic physics , physics , molecule , organic chemistry , computer science , embedded system
Several σ‐hole and π‐hole tetrel‐bonded complexes with a base H 2 CX (X=O, S, Se) have been studied, in which TH 3 F (T=C−Pb) and F 2 TO (T=C and Si) act as the σ‐hole and π‐hole donors, respectively. Generally, these complexes are combined with a primary tetrel bond and a weak H‐bond. Only one minimum tetrel‐bonded structure is found for TH 3 F, whereas two minima tetrel‐bonded complexes for some F 2 TO. H 2 CX is favorable to engage in the π‐hole complex with F 2 TO relative to TH 3 F in most cases, and this preference further expands for the Si complex. Particularly, the double π‐hole complex between F 2 SiO and H 2 CX (X=S and Se) has an interaction energy exceeding 500 kJ/mol, corresponding to a covalent‐bonded complex with the huge orbital interaction and polarization energy. Both the σ‐hole interaction and the π‐hole interaction are weaker for the heavier chalcogen atom, while the π‐hole interaction involving F 2 TO (T=Ge, Sn, and Pb) has an opposite change. Both types of interactions are electrostatic in nature although comparable contributions from dispersion and polarization are respectively important for the weaker and stronger interactions.