Types of noncovalent bonds within complexes of thiazole with CF4 and SiF4

Abstract

The five-membered heteroaromatic thiazole molecule contains a number of electron-rich regions that could attract an electrophile, namely the N and S lone pairs that lie in the molecular plane, and π-system areas above the plane. The possibility of each of these sites engaging in a tetrel bond (TB) with CF₄ and SiF₄, as well as geometries that encompass a CH⋯F H-bond, was explored via DFT calculations. There are a number of minima that occur in the pairing of thiazole with CF₄ that are very close in energy, but these complexes are weakly bound by less than 2 kcal mol⁻¹ and the presence of a true TB is questionable. The inclusion of zero-point vibrational energies alters the energetic ordering, which is further modified when entropic effects are added. The preferred geometry would thus be sensitive to the temperature of an experiment. Replacement of CF₄ by SiF₄ leaves intact most of the configurations, and their tight energetic clustering, the ordering of which is again altered as the temperature rises. But there is one exception in that by far the most tightly bound complex involves a strong Si⋯N TB between SiF₄ and the lone pair of the thiazole N, with an interaction energy of 30 kcal mol⁻¹. Even accounting for its high deformation energy and entropic considerations, this structure remains as clearly the most stable at any temperature.