Cooperative effects between tetrel bond and other σ–hole bond interactions: a comparative investigation

Abstract

Covalently bonded atoms of Groups IV–VII tend to have anisotropic charge distributions, the electronic densities being less on the extensions of the bonds (σ–holes) than in the intervening regions. These σ–holes often give rise to positive electrostatic potentials through which the atom can interact attractively and highly directionally with negative sites. In this work, cooperative effects between tetrel bond and halogen/chalcogen/pnicogen bond interactions are studied in multi-component YH₃M···NCX···NH₃ complexes, where Y = F, CN; M = C, Si and X = Cl, SH and PH₂. These effects are analysed in detail in terms of the structural, energetic, charge-transfer and electron density properties of the complexes. The nature of the σ–hole bonds is unveiled by quantum theory of atoms in molecules and natural bond orbital theory. A favourable cooperativity is found with values that range between −0.34 and −1.15 kcal/mol. Many-body decomposition of interaction energies indicate that two-body energy term is the most important source of the attraction, which its contribution accounts for 87%–96% of the total interaction energy.

Keywords:

• non-covalent bond
• halogen bond
• pnicogen bond
• chalcogen bond
• electrostatic potential

Acknowledgements

This work has been supported by University of Maragheh through a research fund.

Disclosure statement

No potential conflict of interest was reported by the authors.

Supplemental data

Supplemental data for this article can be accessed at http://dx.doi.org/10.1080/00268976.2015.1053550.

Additional information

Funding

University of Maragheh