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Anion⋅⋅⋅Si Interactions in an Inverse Sandwich Complex: A Computational Study
Author(s) -
Robertazzi Arturo,
Platts James A.,
Gamez Patrick
Publication year - 2014
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.201400018
Subject(s) - supramolecular chemistry , density functional theory , chemistry , hydrogen bond , molecule , ring (chemistry) , crystallography , computational chemistry , atoms in molecules , ion , electron density , perturbation theory (quantum mechanics) , binding energy , chemical physics , topology (electrical circuits) , electron , crystal structure , atomic physics , physics , organic chemistry , quantum mechanics , mathematics , combinatorics
Combination of an electron‐rich molecule (e.g. chloride anion or nitrile group) with a chlorinated cyclohexasilane ring produces a supramolecular inverse sandwich complex formed by two guests (Cl − or RC≡N) strongly bonded to both faces of a planar host (Si 6 ring). In‐depth theoretical studies were carried out to investigate the nature of the bonding interactions that generate such a stable complex. Second‐order Møller–Plesset perturbation theory (MP2) calculations confirmed that the presence of the Cl substituents is fundamental to the stability of the supramolecular assemblies. The density functional theory (DFT) functional wB97XD gave an estimation of the contribution of dispersion interactions to the binding energy. These interactions become more important as the Cl atoms of the rings are systematically replaced by methyl groups or hydrogen atoms. Analysis of the topology of the electron density and the reduced density gradient gave insight into the binding of the studied supramolecular assemblies.