Theoretical study on the noncovalent interactions involving triplet diphenylcarbene.

Chunhong Zhao,Aiting Shan,Xueying Zhang,Hui Lin,Xiaoyan Li,Shaofu Guo

doi:10.1007/s00894-021-04838-6

Abstract

The properties of some types of noncovalent interactions formed by triplet diphenylcarbene (DPC3) have been investigated by means of density functional theory (DFT) calculations and quantum theory of atoms in molecule (QTAIM) studies. The DPC3···LA (LA = AlF3, SiF4, PF5, SF2, ClF) complexes have been analyzed from their equilibrium geometries, binding energies, and properties of electron density. The triel bond in the DPC3···AlF3 complex exhibits a partially covalent nature, with the binding energy-65.7 kJ/mol. The tetrel bond, pnicogen bond, chalcogen bond, and halogen bond in the DPC3···LA (LA = SiF4, PF5, SF2, ClF) complexes show the character of a weak closed-shell noncovalent interaction. Polarization plays an important role in the formation of the studied complexes. The strength of intermolecular interaction decreases in the order LA = AlF3 > ClF > SF2 > SiF4 > PF5. The electron spin density transfers from the radical DPC3 to ClF and SF2 in the formation of halogen bond and chalcogen bond, but for the DPC3···AlF3/SiF4/PF5 complexes, the transfer of electron spin density is minimal.

Highlights

The study of noncovalent interactions has been a hot topic in supramolecular chemistry, molecular recognition and materials science [1]
The properties of some types of noncovalent interactions formed by triplet diphenylcarbene (DPC3) have been investigated by means of density functional theory (DFT) calculations and quantum theory of atoms in molecules (QTAIM) studies
The tetrel bond, pnicogen bond, chalcogen bond and halogen bond in the DPC3···LA (LA = SiF4, PF5, SF2, ClF) complexes show the character of a weak closed-shell noncovalent interaction

Summary

Introduction

The study of noncovalent interactions has been a hot topic in supramolecular chemistry, molecular recognition and materials science [1]. The concepts of σ-holes or π-holes that have been pointed out by Politzer and Clark et al [6,7,8,9,10,11,12] reflect the fact that covalently-bonded atom tends to have anisotropic electronic densities, with regions of higher and lower density. A σ-hole or π-hole is a region of lower electronic density along the extension of a covalently-bonded atom, or perpendicular to a planar portion of a molecule. This region gives rise to positive electrostatic potential, can be used as a Lewis acid to interact attractively with the rich electronic center (lone pairs, π electrons, anions, etc.) of a Lewis base. Noncovalent interactions involving σhole or σ-lump on a coinage metal have been reported [23,24,25]

Methods

Results

Conclusion