Nucleophilicities of Lewis Bases B and Electrophilicities of Lewis Acids A Determined from the Dissociation Energies of Complexes B⋯A Involving Hydrogen Bonds, Tetrel Bonds, Pnictogen Bonds, Chalcogen Bonds and Halogen Bonds

Ibon Alkorta, Anthony Legon

Research output: Contribution to journalArticle (Academic Journal)peer-review

13 Citations (Scopus)
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Abstract

It is shown that the dissociation energy De for the process B⋯A = B + A for 250 complexes B⋯A composed of 11 Lewis bases B (N2, CO, HC≡CH, CH2=CH2, C3H6, PH3, H2S, HCN, H2O, H2CO and NH3) and 23 Lewis acids (HF, HCl, HBr, HC≡CH, HCN, H2O, F2, Cl2, Br2, ClF, BrCl, H3SiF, H3GeF, F2CO, CO2, N2O, NO2F, PH2F, AsH2F, SO2, SeO2, SF2, and SeF2) can be represented to good approximation by means of the equation De=c′NBEA , in which NB is a numerical nucleophilicity assigned to B, EA is a numerical electrophilicity assigned to A, and c′ is a constant, conveniently chosen to have the value 1.00 kJ mol−1 here. The 250 complexes were chosen to cover a wide range of non-covalent interaction types, namely: (1) the hydrogen bond; (2) the halogen bond; (3) the tetrel bond; (4) the pnictogen bond; and (5) the chalcogen bond. Since there is no evidence that one group of non-covalent interaction was fitted any better than the others, it appears the equation is equally valid for all the interactions considered and that the values of NB and EA so determined define properties of the individual molecules. The values of NB and EA can be used to predict the dissociation energies of a wide range of binary complexes B⋯A with reasonable accuracy.
Original languageEnglish
Pages (from-to)1786-1799
Number of pages14
JournalMolecules
Volume22
Early online date23 Oct 2017
DOIs
Publication statusPublished - Oct 2017

Keywords

  • noncovalent bonds
  • binary complexes
  • dissociation energies
  • nucleophilicity
  • electrophilicity
  • ab initio calculations
  • geometry

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