The complexes between borazine and TH3F/F2TO/H2TO (T=C, Si, Ge) are investigated with high-level quantum chemical calculations. Borazine has three sites of negative electrostatic potential: the N atom, the ring center, and the H atom of the B-H bond, while TH3F and F2TO/H2TO provide the σ-hole and π-hole, respectively, for the tetrel bond. The N atom of borazine is the favored site for both the σ and π-hole tetrel bonds. Less stable dimers include a σ-tetrel bond to the borazine ring center and to the BH proton. The π-hole tetrel-bonded complexes are more strongly bound than aretheirσ-hole counterparts. Due to the coexistence of both T···N tetrel and B···O triel bonding, the complexes of borazine with F2TO/H2TO (T= Si and Ge) are very stable, with interaction energies up to -108 kcal/mol. The strongly bonded complexes are accompanied by substantial net charge transfer from F2TO/H2TO to borazine. Polarization energy makes a contribution comparable with electrostatic for the moderately or strongly bonded complexes but is small in their weaker analogues.
This is the peer reviewed version of the following article: Zhang, J., Hu, Q., Li, Q., Scheiner, S. I., Liu, S. (2019). Comparison of σ-hole and π-hole tetrel bonds in complexes of borazine with TH3F and F2TO/H2TO (T=C, Si, Ge). International Journal of Quantum Chemistry, 119(11), e25910. https://onlinelibrary.wiley.com/doi/abs/10.1002/qua.25910, which has been published in final form at https://doi.org/10.1002/qua.25910. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.