J. Phys. Chem. A 123, 7124−7132 (2019)

DOI: 10.1021/acs.jpca.9b06051

Weak Interactions Get Strong: Synergy between Tetrel and AlkalineEarth Bonds

Weak and strong noncovalent interactions such as tetrel bonds and alkaline-earth bonds, respectively, cooperate and get reinforced when acting together in ternary complexes of general formula RN··· SiH3F···MY, where MY is a Be or Mg derivative and RN is a N-containing Lewis base with different hybridization patterns. Cooperativity has been studied in the optimized MP2/aug′-cc-pVTZ ternary complexes by looking at changes on geometries, binding energies, 29Si NMR chemical shifts, and topological features according to the atoms in molecules theoretical framework. Our study shows that cooperativity in terms of energy is in general significant: more than 40 kJ/mol, and up to 83.6 kJ/mol in the most favorable case. The weakest the isolated interaction, the strongest the reinforcement in the ternary complex; in this sense, the tetrel bond is shortened enormously, between 0.3 and 0.6 Å. This dramatic reinforcement of the tetrel bond is also nicely reflected in the positive variations of the 29Si chemical shifts in all the ternary complexes. At the same time the ternary complexes are characterized by the presence of totally planar silyl group, due to the pentacoordination of the Si atom. Both the hybridization of the N base and the geometry imposed by the alkaline-earth ligands have a strong influence on the binding energies, as they modify the donor ability of N and the Lewis acid character of the alkaline-earth metal.