Issue 48, 2016

The intrinsic strength of the halogen bond: electrostatic and covalent contributions described by coupled cluster theory

Abstract

36 halogen-bonded complexes YX⋯ARm (X: F, Cl, Br; Y: donor group; ARm acceptor group) have been investigated at the CCSD(T)/aug-cc-pVTZ level of theory. Binding energies, geometries, NBO charges, charge transfer, dipole moments, electrostatic potential, electron and energy density distributions, difference density distributions, vibrational frequencies, local stretching and bending force constants, and relative bond strength orders n have been calculated and used to order the halogen bonds according to their intrinsic strength. Halogen bonding is found to arise from electrostatic and strong covalent contributions. It can be strengthened by H-bonding or lone pair delocalization. The covalent character of a halogen bond increases in the way 3c-4e (three-center-four-electron) bonding becomes possible. One can characterize halogen bonds by their percentage of 3c-4e bonding. FCl–phosphine complexes can form relatively strong halogen bonds provided electronegative substituents increase the covalent contributions in form of 3c-4e halogen bonding. Binding energies between 1 and 45 kcal mol−1 are calculated, which reflects the large variety in halogen bonding.

Graphical abstract: The intrinsic strength of the halogen bond: electrostatic and covalent contributions described by coupled cluster theory

Supplementary files

Article information

Article type
Paper
Submitted
27 Sep 2016
Accepted
17 Nov 2016
First published
17 Nov 2016

Phys. Chem. Chem. Phys., 2016,18, 33031-33046

The intrinsic strength of the halogen bond: electrostatic and covalent contributions described by coupled cluster theory

V. Oliveira, E. Kraka and D. Cremer, Phys. Chem. Chem. Phys., 2016, 18, 33031 DOI: 10.1039/C6CP06613E

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