Cooperativity between H-bonds and tetrel bonds. Transformation of a noncovalent C⋯N tetrel bond to a covalent bond.

The dimers and trimers formed by imidazole (IM) and F 2 TO (T = C, Si, Ge) are studied by ab initio calculations. IM can engage in either a NH⋯O H-bond with F 2 TO or a T⋯N tetrel bond (TB) with the π-hole above the T atom. The latter is a true noncovalent TB for T = C but is a much shorter and stronger covalent bond with F 2 SiO or F 2 GeO. When a second IM is added, the cooperativity emerging from its H-bond with the first IM makes it a stronger nucleophile, leading to two minima with F 2 CO. The first structure contains a long noncovalent C⋯O TB and there is a much shorter covalent bond in the other, with a small energy barrier separating them. The same sort of double minimum occurs when the two IM units are situated parallel to one another in a stacked geometry.