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Intramolecular Si⋅⋅⋅O Tetrel Bonding: Tuning of Substituents and Cooperativity
Author(s) -
Wei Yuanxin,
Li Qingzhong,
Yang Xin,
McDowell Sean A. C.
Publication year - 2017
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201702280
Subject(s) - intramolecular force , cooperativity , hydrogen bond , interaction energy , chemistry , crystallography , molecule , binding energy , electron density , density functional theory , computational chemistry , stereochemistry , electron , atomic physics , physics , organic chemistry , biochemistry , quantum mechanics
A computational study of an intramolecular tetrel bond in o‐methoxymethyl‐PhSiF 3 (P) and its derivatives at the 4 and 5 positions by substituents X (4‐X−P and 5‐X−P, X=F, Cl, Br, NO 2 , OH, and NH 2 ) has been performed. The Si⋅⋅⋅O interaction is characterized by the short Si⋅⋅⋅O distance, strong orbital interaction, large interaction energy, and negative energy density. Substituents do not greatly affect the strength of the intramolecular Si⋅⋅⋅O interaction but some interesting results are obtained. The electron‐donating group in 5‐OH−P strengthens this interaction more than the electron‐withdrawing group in 5‐NO 2 ‐P. The interaction energy of the intramolecular Si⋅⋅⋅O interaction has been computed with three different methods and the most reliable result is obtained with an expression using the potential energy density at the Si⋅⋅⋅O bond critical point. When a water molecule is attached to P to form an OH⋅⋅⋅F hydrogen bond, the intramolecular Si⋅⋅⋅O interaction is greatly enhanced yielding an interaction energy up to ∼12 kcal mol −1 .