Examining a Transition from Supramolecular Halogen Bonding to Covalent Bonds: Topological Analysis of Electron Densities and Energies in the Complexes of Bromosubstituted Electrophiles.

ABSTRACT: The transition from weak (noncovalent) interactions to fully developed covalent bonds is examined using the quantum theory of atoms in molecules in a series of halogen-bonded (XB) complexes of bromosubstituted electrophiles, RBr, with 1,4-diazabicyclo[2.2.2]octane (DABCO) and Cl^- and Br^- anions. The gradual decrease in the XB lengths in these associations, d _Br···Y (where Y = Cl^-, Br^-, or N), was accompanied by the exponential increase in the binding energies and charge transfer, as well as electron densities and magnitudes of the kinetic and potential energy densities at the bond critical points (BCPs) on the Br···Y bond path. These indices, as well as characteristics of the adjacent bonds in the XB donor, followed remarkably c

SUBMITTER: Miller DK 

PROVIDER: S-EPMC8444318 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature