Cooperative Effects in Weak Interactions: Enhancement of Tetrel Bonds by Intramolecular Hydrogen Bonds.

Cristina Trujillo,José Elguero,Goar Sánchez-Sanz,Ibon Alkorta

doi:10.3390/molecules24020308

Abstract

A series of silyl and germanium complexes containing halogen atoms (fluorine and chlorine atoms) and exhibiting tetrel bonds with Lewis bases were analyzed by means of Møller-Plesset computational theory. Binding energies of germanium derivatives were more negative than silicon ones. Amongst the different Lewis bases utilized, ammonia produced the strongest tetrel bonded complexes in both Ge and Si cases, and substitution of the F atom by Cl led to stronger complexes with an ethylene backbone. However, with phenyl backbones, the fluorosilyl complexes were shown to be less stable than the chlorosilyl ones, but the opposite occurred for halogermanium complexes. In all the cases studied, the presence of a hydroxyl group enhanced the tetrel bond. That effect becomes more remarkable when an intramolecular hydrogen bond between the halogen and the hydrogen atom of the hydroxyl group takes places.

Highlights

One of the major achievements in contemporary chemistry was the introduction by Jean-MarieLehn of supramolecular chemistry [1]
These non-covalent interactions has been categorised based on the interacting atoms involved: hydrogen bonds [3,4], halogen bonds [5], hydride bonds [6,7], pnictogen bonds [8,9,10,11,12,13], chalcogen interactions [14,15,16,17,18] and tetrel bonds [19,20,21,22]
The latter, tetrel bonds, are defined, analogous to halogen bonds, as interactions between electron donors and tetrel atoms (C, Si and Ge), in which the tetrel atom acts as an electron acceptor, usually through an electron-deficient outer lobe of a p orbital, called a σ-hole [23] by Politzer and Murray [24,25,26], which is formed in the tetrel atom, especially when the atom bonded to the tetrel is highly electronegative

Summary

Introduction

One of the major achievements in contemporary chemistry was the introduction by Jean-MarieLehn of supramolecular chemistry [1]. There are numerous weak interactions, known as non-covalent interactions, and they have been shown to be of the upmost importance across different domains including biology, chemistry and material science [2] These non-covalent interactions has been categorised based on the interacting atoms involved: hydrogen bonds [3,4], halogen bonds [5], hydride bonds [6,7], pnictogen bonds [8,9,10,11,12,13], chalcogen interactions [14,15,16,17,18] and tetrel bonds [19,20,21,22]. It has been shown that interactions through σ-holes are mainly driven by the electrostatic interaction term [27,28,29,30,31,32,33,34,35,36,37,38]

Methods

Results

Conclusion