An ab initio study of some halogen-bonded complexes containing cyclic ethers

Abstract

The binary complexes formed between the dihalogens fluorine, chlorine and bromine, and the cyclic ethers oxirane, oxetane, tetrahydrofuran and tetrahydropyran, have been studied by means of ab initio calculations at the second-order level of Møller–Plesset perturbation theory. The properties of interest are the interaction energies, the intermolecular geometries, the perturbations of the intramolecular dihalogen and ether geometries, the wavenumber shifts of the dihalogen and ether molecules, and the variations of the natural atomic charges resulting from complexation. The trends observed are discussed in terms of the physical properties of the interacting monomers, such as the polarizabilities of the dihalogen molecules and the gas phase basicities of the ethers.