The Tetrel Bonds of Hypervalent Halogen Compounds

Zhihao Niu; Sean A C McDowell; Qingzhong Li

doi:10.3390/molecules28207087

The Tetrel Bonds of Hypervalent Halogen Compounds

Molecules. 2023 Oct 14;28(20):7087. doi: 10.3390/molecules28207087.

Authors

Zhihao Niu¹, Sean A C McDowell², Qingzhong Li¹

Affiliations

¹ The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, China.
² Department of Biological and Chemical Sciences, The University of the West Indies, Cave Hill Campus, Bridgetown BB11000, Barbados.

Abstract

The tetrel bond between PhXF₂Y(TF₃) (T = C and Si; X = Cl, Br, and I; Y = F and Cl) and the electron donor MCN (M = Li and Na) was investigated at the M06-2X/aug-cc-pVDZ level of theory. As the electronegativity of the halogen atom X increases, the strength of the tetrel bond also increases, but as the electronegativity of the halogen atom Y increases, the strength of the tetrel bond decreases. The magnitude of the interaction energy in most -CF₃ complexes was found to be less than 10 kcal/mol, but to exceed 11 kcal/mol for PhClF₂Cl(CF₃)⋯NCNa. The tetrel bond is greatly enhanced when the -SiF₃ group interacts with LiCN or NaCN, with the largest interaction energy approaching 100 kcal/mol and displaying a covalent Si⋯N interaction. Along with this enhancement, the Si⋯N distance was found to be less than the X-Si bond length, the -SiF₃ group to be closer to the N atom, and in most -SiF₃ systems, the X-Si-F angle to be less than 90°; the -SiF₃ group therefore undergoes inversion and complete transfer in some systems.

Keywords: group transfer; hypervalent halogen; tetrel bond; σ-hole.

Abstract

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