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Strong dispersion interaction of the carbanionic center in methide anion derivatives with halogen atom of metal halides

Authors
  • Isaev, Alexander N1
  • 1 Russian Academy of Sciences, Leninsky pr. 47, Moscow, 119991, Russia , Moscow (Russia)
Type
Published Article
Journal
Journal of Chemical Sciences
Publisher
Springer India
Publication Date
Feb 08, 2022
Volume
134
Issue
1
Identifiers
DOI: 10.1007/s12039-021-02020-2
Source
Springer Nature
Keywords
Disciplines
  • Regular Article
License
Yellow

Abstract

Using the MP2/aug-cc-pVTZ method, quantum chemical calculations of binary complexes with intermolecular C(sp3)...Hal−M (Hal = F, Cl, Br; M = Li, Na, Cu, Mg) bonds formed by the methide anion and its derivatives with metal halides were carried out. The calculations showed that the binding energy in the carbanion complex is higher, the greater the distance between the monomers. The least stable complexes form the strongest partially covalent intermolecular bond with the largest values of electron density at the bond (3, − 1) critical point of the C...Hal contact. The unusual properties of carbanion complexes analyzed in this study are determined by an increase in the energy of electron correlation Ecorr with increasing the intermolecular distance; Ecorr can exceed 50 kcal/mol. The MP2 and CCSD(T) levels of the theory predict a linear relationship between Ecorr values and binding energies.Graphical abstractSynopsis: Dramatic changes in the stability of carbanion complexes with the replacement of a hydrogen atom by lithium.

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