From ‘halogen’ to ‘tetrel’ bonds: matrix isolation IR spectroscopic and quantum mechanical studies of the effect of central atom substitution in donor tetrahalogens on binary complex formation with formic acid

Abstract

Binary complex formation between silicon tetrachloride (SiCl₄) and formic acid (FA) has been observed in an argon matrix environment. Such complex formation manifests as spectral shifts in signature vibrations of the latter, namely the ν_CO, ν_C–O and ν_O–H vibrations. Quantum chemical calculations reveal that the most stable conformers of the complex involve predominantly the tetrel bond, which has been defined in existing literature as a variant of the “σ-hole” interactions. Here, regions of positive electrostatic potential on the tetrahedral face of SiCl₄ act as electrophilic centers (σ-hole) to which the nucleophilic carbonyl group of FA is able to bind. Atoms-in-molecules analysis predicts a bond critical point along the non-covalent contact between the tetrel atom Si and the carbonyl oxygen on FA, corroborating the presence of the tetrel bond. The hyperconjugative interaction parameters at the binding interface obtained from Natural Bond Orbital (NBO) analysis are also consistent with such observations. Although apparently similar to SiCl₄, there are noticeable differences in the binding preferences of the lower homologue carbon tetrachloride (CCl₄). The binary complexes of the latter with the same FA acceptor molecule have been previously shown to involve halogen bonded, rather than tetrel bonded interactions (Banerjee and Bhattacharya, Spectrochim. Acta Mol. and Biomol. Spectrosc., 2021, 250, 119355). Such variations in the nature of non-covalent interactions of these tetrahalogens are attributed to differences in the distribution of electronic charge density surrounding the central tetrel atom, as obtained from mappings of their electrostatic potential surfaces. Our combined experimental and theoretical findings therefore provide direct evidence of the growing propensity of tetrel atoms to engage in tetrel bonding as we move lower down Group 14, and re-assert the reluctance of the smaller and more electronegative carbon atom to serve as a tetrel bond participant.