Ability of the Spectroscopic Properties of the P═Se Bond of a Base to Assess Noncovalent Bond Strength.

Abstract

The viability of the P═Se bond to serve as a monitor of the strength of a noncovalent bond was tested in the context of the (CH₃)₃PSe molecule. Density functional theory (DFT) computations paired this base with a collection of Lewis acids that spanned hydrogen, halogen, chalcogen, pnicogen, and tetrel bonding interactions and covered a wide range of bond strengths. A very strong linear correlation was observed between the interaction energy and the nuclear magnetic resonance (NMR) ¹J(PSe) coupling constant, which could serve as an accurate indicator of bond strength. Also correlating very well with the interaction energy is the stretch of the P═Se bond caused by complexation and the red shift of its stretching frequency. Moderate correlations arise in the chemical shifts of the P and Se nuclei. The σ-hole depth on the Lewis acid is poorly correlated with the energetics, and the same is true for the full electrostatic contribution to the bond energy. Of the various components, it is the polarization energy that correlates most closely with the interaction energy.