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Issue 28, 2020
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An ab initio investigation of alkali–metal non-covalent bonds B⋯LiR and B⋯NaR (R = F, H or CH3) formed with simple Lewis bases B: the relative inductive effects of F, H and CH3

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Abstract

The alkali–metal bonds formed by simple molecules LiR and NaR (R = F, H or CH3) with each of the six Lewis bases B = OC, HCN, H2O, H3N, H2S and H3P were investigated by ab initio calculations at the CCSD(T)/AVTZ and CCSD(T)/awCVTZ levels of theory with the aim of characterising this type of non-covalent interaction. In some complexes, two minima were discovered, especially for those involving the NaR. The higher-energy minimum (referred to as Type I) for a given B was found to have geometry that is isomorphous with that of the corresponding hydrogen-bonded analogue B⋯HF. The lower-energy minimum (when two were present) showed evidence of a significant secondary interaction of R with the main electrophilic region of B (Type II complexes). Energies DCBSe for dissociation of the complexes into separate components were found to be directly proportional to the intermolecular stretching force constant kσ The value of DCBSe could be partitioned into a nucleophilicity of B and an electrophilicity of LiR or NaR, with the order ELiHELiF = ELiCH3 for the LiR and ENaF > ENaHENaCH3 for the NaR. For a given B, the order of the electrophilicities is ELiR > ENaR, which presumably reflects the fact that Li+ is smaller than Na+ and can approach the Lewis base more closely. A SAPT analysis revealed that the complexes B⋯LiR and B⋯NaR have larger electrostatic contributions to De than do the hydrogen- and halogen-bonded counterparts B⋯HCl and B⋯ClF.

Graphical abstract: An ab initio investigation of alkali–metal non-covalent bonds B⋯LiR and B⋯NaR (R = F, H or CH3) formed with simple Lewis bases B: the relative inductive effects of F, H and CH3

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Supplementary files

Article information


Submitted
18 May 2020
Accepted
23 Jun 2020
First published
25 Jun 2020

Phys. Chem. Chem. Phys., 2020,22, 16421-16430
Article type
Paper

An ab initio investigation of alkali–metal non-covalent bonds B⋯LiR and B⋯NaR (R = F, H or CH3) formed with simple Lewis bases B: the relative inductive effects of F, H and CH3

I. Alkorta, J. G. Hill and A. C. Legon, Phys. Chem. Chem. Phys., 2020, 22, 16421
DOI: 10.1039/D0CP02697B

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