For inorganic benzenes CNX and BOX (X = H, F, CN), the positive electrostatic potentials (π-hole) were discovered above and below the inorganic benzene ring center. Then, the π-hole interactions between the inorganic benzenes and NCH have been designed and investigated by MP2/aug-cc-pVDZ calculations. In this paper, the termolecular complexes BOX···NCH···NCH, CNX···NCH···NCH (X = H, F, CN) were also designed to illustrate the enhancing effects of the H···N hydrogen bond on the π-hole interactions. The π-hole interaction energy was influenced by the strength of different electron-withdrawing substituents of inorganic benzenes, gradually increasing in the order of X = H, F, CN. What's more, the π electron densities account for 71~88% of the total electron densities, indicating the strength of interaction energy is mainly determined by π-type electron densities. Graphical abstract The termolecular complexes BOX···NCH···NCH, CNX···NCH···NCH (X = H, F, CN) were designed to illustrate the enhancing effects of the H···N hydrogen bond on the π-hole interactions.

Carbon bond and hydrogen bond are common noncovalent interactions; although recent advances on these interactions have been achieved in both the experimental and computational aspects, little is known about the conversion mechanism between them. Here, MP2 calculations with aug-cc-pVDZ basis set (aug-cc-pVDZ-pp for element Sn) were used to optimize the geometric configurations of the hydrogen-bonded complexes MH 3 F···HCN (M = C, Si, Ge, and Sn), carbon-bonded complexes HCN···MH 3 F (M = C, Si, Ge, and Sn), and transition states; the conversion mechanism between these two types of interactions has been carried out. The molecular electrostatic potential, especially the σ-hole, is directly related to the flatten degree of intrinsic reaction coordinate (IRC) curve. The energy barriers from the hydrogen-bonded complexes to the carbon-bonded complexes are 6.99, 7.73, 10.56, and 13.59 kJ·mol –1 . The energy barriers from the carbon-bonded complexes to the hydrogen-bonded complexes are 4.65, 7.81, 9.10, and 13.04 kJ·mol –1 . The breakage and formation of the bonds along the reaction paths have been discussed by the topological analysis of electronic density. The energy barriers are obviously related to the width of the structure transition region (STR). For the first derivative curve of IRC energy surface versus reaction coordinate, there is a maximum peak and a minimum peak, reflecting the structural transition states in the ring STRs.