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Tetrel bonds between PhSiF 3 /PhTH 3 (T = Si, Ge, Sn) and H 3 ZO (Z = N, P, As): A pentacoordinate silicon (IV) complex
Author(s) -
Xu HuiLi,
Cheng JianBo,
Li HaiBei,
Yang Xin,
Li QingZhong
Publication year - 2018
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25660
Subject(s) - antibonding molecular orbital , crystallography , organosilicon , chemistry , lone pair , silicon , atom (system on chip) , covalent bond , atomic orbital , stereochemistry , atomic physics , physics , molecule , organic chemistry , quantum mechanics , computer science , embedded system , electron
The nature of the complexes PhTH 3 H 3 ZO and PhSiF 3 H 3 ZO (T = Si, Ge, and Sn; Z = N, P, and As) has been investigated at the MP2/aug’‐cc‐pVTZ(PP) level. These complexes are primarily stabilized by one T···O tetrel bond. Interaction energies of these complexes vary from 11 to 220 kJ/mol, and T···O separations from 1.89 to 3.09 Å. Charge transfer from the O lone pair into the CT and TH σ* antibonding orbitals leads to the stabilization of these complexes. The T···O tetrel bond between PhTH 3 /PhSiF 3 and H 3 NO exhibits a significant degree of covalence, characterized by the large interaction energy, negative energy density, and large charge transfer. Furthermore, a pentacoordinate silicon (IV) complex is formed in PhSiF 3 H 3 NO with the Si···O distance almost close to the length of SiO bond. This indicates that the oxygen atom in N‐oxides shows a strong affinity to the silicon atom in organosilicon compounds.