Comparative Strengths of Tetrel, Pnicogen, Chalcogen, and Halogen Bonds and Contributing Factors.

Wenbo Dong,Steve Scheiner,Qingzhong Li

doi:10.3390/molecules23071681

Wenbo Dong, Steve Scheiner + Show 1 more

Open Access

https://doi.org/10.3390/molecules23071681

Copy DOI

Abstract

Ab initio calculations are employed to assess the relative strengths of various noncovalent bonds. Tetrel, pnicogen, chalcogen, and halogen atoms are represented by third-row atoms Ge, As, Se, and Br, respectively. Each atom was placed in a series of molecular bonding situations, beginning with all H atoms, then progressing to methyl substitutions, and F substituents placed in various locations around the central atom. Each Lewis acid was allowed to engage in a complex with NH3 as a common nucleophile, and the strength and other aspects of the dimer were assessed. In the context of fully hydrogenated acids, the strengths of the various bonds varied in the pattern of chalcogen > halogen > pnicogen ≈ tetrel. Methyl substitution weakened all bonds, but not in a uniform manner, resulting in a greatly weakened halogen bond. Fluorosubstitution strengthened the interactions, increasing its effect as the number of F atoms rises. The effect was strongest when the F atom lay directly opposite the base, resulting in a halogen > chalcogen > pnicogen > tetrel order of bond strength. Replacing third-row atoms by their second-row counterparts weakened the bonds, but not uniformly. Tetrel bonds were weakest for the fully hydrogenated acids and surpassed pnicogen bonds when F had been added to the acid.

Highlights

A revolution of sorts, albeit a gradual one, occurred in the field of noncovalent interactions as it became progressively more apparent that the venerable H-bond was not completely unique
The interaction, whether an H or halogen bond, is not entirely electrostatic as it contains other elements, such as charge transfer and dispersion, but this charge distribution voided the argument that a halogen atom must necessarily repel an incoming nucleophile
In the fully hydrogenated series of Lewis acids, the strengths of the various bonds varied in the pattern chalcogen > halogen > pnicogen > tetrel, the last two were reversed if the level of calculation was raised from MP2 to CCSD(T)

Summary

Introduction

A revolution of sorts, albeit a gradual one, occurred in the field of noncovalent interactions as it became progressively more apparent that the venerable H-bond was not completely unique. The first class of atoms that fit this criterion was the halogens [1,2,3,4,5,6,7,8,9,10] The ability of these very electronegative atoms to replace an H atom was deemed counterintuitive at first, as the polarity of the R-H bond, placing a partial positive charge on the proton, was considered a prime ingredient of the classic H-bond. While there is an equatorial band of negative electrostatic potential surrounding the X atom in a R-X bond, there is a positive polar region situated directly opposite the R atom This positive area, frequently referred to as a σ-hole, can attract an approaching nucleophile in precisely the same way the partially positive charge surrounding the proton of a H-bond can [11,12]. The interaction, whether an H or halogen bond, is not entirely electrostatic as it contains other elements, such as charge transfer and dispersion, but this charge distribution voided the argument that a halogen atom must necessarily repel an incoming nucleophile

Results

Discussion

Conclusion