Tetrel Bonds with π-Electrons Acting as Lewis Bases—Theoretical Results and Experimental Evidences

MP2/aug-cc-pVTZ calculations were carried out for the ZFH(3)-B complexes (Z = C, Si, Ge, Sn and Pb; B = C(2)H(2), C(2)H(4), C(6)H(6) and C(5)H(5)(-); relativistic effects were taken into account for Ge, Sn and Pb elements). These calculations are supported by other approaches; the decomposition of the energy of interaction, Quantum Theory of Atoms in Molecules (QTAIM) and Natural Bond Orbital (NBO) method. The results show that tetrel bonds with π-electrons as Lewis bases are classified as Z···C links between single centers (C is an atom of the π-electron system) or as Z···π interactions where F‒Z bond is directed to the mid-point (or nearly so) of the CC bond of the Lewis base. The analogous systems with Z···C/π interactions were found in the Cambridge Structural Database (CSD). It was found that the strength of interaction increases with the increase of the atomic number of the tetrel element and that for heavier tetrel elements the ZFH(3) tetrahedral structure is more deformed towards the structure with the planar ZH(3) fragment. The results of calculations show that the tetrel bond is sometimes accompanied by the Z-H···C hydrogen bond or even sometimes the ZFH(3)-B complexes are linked only by the hydrogen bond interaction.