Jump to main content
Jump to site search

Issue 3, 2015
Previous Article Next Article

Using beryllium bonds to change halogen bonds from traditional to chlorine-shared to ion-pair bonds

Author affiliations

Abstract

Ab initio MP2/aug′-cc-pVTZ calculations have been carried out to investigate the structures, binding energies, and bonding characteristics of binary complexes HFBe:FCl, R2Be:FCl, and FCl:N-base, and of ternary complexes HFBe:FCl:N-base and R2Be:FCl:N-base for R = H, F, Cl; N-base = NH3, NHCH2, NCH. Dramatic synergistic cooperative effects have been found between the Be⋯F beryllium bonds and the Cl⋯N halogen bonds in ternary complexes. The Cl⋯N traditional halogen bonds and the Be⋯F beryllium bonds in binary complexes become significantly stronger in ternary complexes, while the F–Cl bond weakens. Charge-transfer from F to the empty p(σ) orbital of Be leads to a bending of the XYBe molecule and a change in the hybridization of Be, which in the limit becomes sp2. As a function of the intrinsic basicity of the nitrogen base and the intrinsic acidity of the Be derivative, the halogen-bond type evolves from traditional to chlorine-shared to ion-pair bonds. The mechanism by which an ion-pair complex is formed is similar to that involved in the dissociative proton attachment process. EOM-CCSD spin–spin coupling constants 1XJ(Cl–N) across the halogen bond in these complexes also provide evidence of the same evolution of the halogen-bond type.

Graphical abstract: Using beryllium bonds to change halogen bonds from traditional to chlorine-shared to ion-pair bonds

Back to tab navigation

Supplementary files

Publication details

The article was received on 09 Oct 2014, accepted on 27 Nov 2014 and first published on 28 Nov 2014


Article type: Paper
DOI: 10.1039/C4CP04574B
Author version available: Download Author version (PDF)
Citation: Phys. Chem. Chem. Phys., 2015,17, 2259-2267
  •   Request permissions

    Using beryllium bonds to change halogen bonds from traditional to chlorine-shared to ion-pair bonds

    I. Alkorta, J. Elguero, O. Mó, M. Yáñez and J. E. Del Bene, Phys. Chem. Chem. Phys., 2015, 17, 2259
    DOI: 10.1039/C4CP04574B

Search articles by author

Spotlight

Advertisements