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Anion-Anion Interactions in Aerogen-Bonded Complexes. Influence of Solvent Environment.

ABSTRACT: Ab initio calculations are applied to the question as to whether a AeX₅^- anion (Ae = Kr, Xe) can engage in a stable complex with another anion: F^-, Cl^-, or CN^-. The latter approaches the central Ae atom from above the molecular plane, along its C₅ axis. While the electrostatic repulsion between the two anions prevents their association in the gas phase, immersion of the system in a polar medium allows dimerization to proceed. The aerogen bond is a weak one, with binding energies less than 2 kcal/mol, even in highly polar aqueous solvent. The complexes are metastable in the less polar solvents THF and DMF, with dissociation opposed by a small energy barrier.

SUBMITTER: Grabarz A

PROVIDER: S-EPMC8067769 | biostudies-literature |

REPOSITORIES: biostudies-literature

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