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Interplay between tetrel and triel bonds in RC 6 H 4 CN⋯MF 3 CN⋯BX 3 complexes: A combined symmetry‐adapted perturbation theory, Møller‐Plesset, and quantum theory of atoms‐in‐molecules study
Author(s) -
Yourdkhani Sirous,
Korona Tatiana,
Hadipour Nasser L.
Publication year - 2015
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24226
Subject(s) - chemistry , atoms in molecules , hypervalent molecule , molecule , intermolecular force , monomer , crystallography , ternary operation , interaction energy , covalent bond , computational chemistry , organic chemistry , polymer , reagent , computer science , programming language
Intermolecular ternary complexes composed of: (1) the centrally placed trifluoroacetonitrile or its higher analogs with central carbon exchanged by silicon or germanium (M = C, Si, Ge), (2) the benzonitrile molecule or its para derivatives on one side, and (3) the boron trifluoride of trichloride molecule (X = F, Cl) on the opposite side as well as the corresponding intermolecular tetrel‐ and triel‐bonded binary complexes, were investigated by symmetry‐adapted perturbation theory (SAPT) and the supermolecular Møller‐Plesset method (MP2) at the complete basis set limit for optimized geometries. A character of interactions was studied by quantum theory of atoms‐in‐molecules (QTAIM). A comparison of interaction energies and QTAIM bond descriptors for dimers and trimers reveals that tetrel and triel bonds increase in their strength if present together in the trimer. For the triel‐bonded complex, this growth leads to a change of the bond character from closed‐shell to partly covalent for Si or Ge tetrel atoms, so the resulting bonding scheme corresponds to a preliminary stage of theS N 2 reaction. Limitations of the Lewis theory of acids and bases were shown by its failure in predicting the stability order of the triel complexes. The necessity of including interaction energy terms beyond the electrostatic component for an elucidation of the nature of σ ‐ and π ‐holes was presented by a SAPT energy decomposition and by a study of differences in monomer electrostatic potentials obtained either from isolated monomer densities, or from densities resulting from a perturbation with the effective field of another monomer. © 2015 Wiley Periodicals, Inc.