Chem. Phys. Lett. 685, 338-343 (2017)

DOI: 10.1016/j.cplett.2017.07.051

Halogen bonding with carbene bases

Ab initio MP2/aug’-cc-pVTZ calculations have been performed to determine the structures and binding energies of complexes formed from five singlet carbene bases acting as electron-pair donors to four ClX acids. Complexes with ClCCH and ClCN are stabilized by traditional halogen bonds. With one exception, complexes with ClNC and ClF are stabilized by (carbene-Cl)+–NC and (carbene-Cl)+–F ion-pair halogen bonds subsequent to chlorine transfer. These complexes have been characterized in terms of their structures, binding energies, charge-transfer energies, bonding properties, and spin-spin coupling constants.

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