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Effects of substitutions in the equatorial position on the stabilities of pentacoordinated silicon anions of ClSi abc OCl − ( a , b , c = H, F, Cl) from theoretical investigation
Author(s) -
Junxi Liang,
Yingxue Wang,
Li Liu
Publication year - 2018
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201700421
Subject(s) - chemistry , electronegativity , crystallography , fluorine , ligand (biochemistry) , computational chemistry , ab initio , basis set , stereochemistry , density functional theory , biochemistry , receptor , organic chemistry
Stability of a series of pentacoordinated silicon anions ClSi abc OCl − ( a , b , c = H, F, Cl) is explored to understand the effects of the substitutions in their equatorial position using DFT and ab initio methods. The basis set used in this work is Dunning's double‐zeta correlation consistent with an extra diffuse function, denoted aug‐cc‐pVDZ. The minima confirmed by vibrational analysis are most often characterized by the five‐coordinated configuration in which the equatorial positions are composed of all combinations of the ligand atoms, hydrogen, chlorine, and fluorine. Our model calculations suggest that stabilization of the pentacoordinated species ClSi abc OCl − is not only well correlated with the collective electronegativity of equatorial atoms abc but also sufficiently govened by the symmetry of molecular structure, in which the more electronegative the substitution, the more symmetric the geometry and the higher the stabilization. We also report the theoretical prediction of hyperconjugative stereoelectronic effect that contributes to the staggered conformation of the studied isomers, which should result in less stability.