# The Impact of Perfluoroalkyl Groups on Phosphane Basicity

## TL;DR

This paper shows that adding perfluoroalkyl groups to phosphane compounds dramatically reduces their basicity, which could impact catalysis and ligand design.

## Contribution

The study reveals unexpectedly low pKaH values for polyfluorinated phosphanes, challenging existing assumptions about their electronic properties.

## Key findings

- Computed pKaH values in acetonitrile for polyfluorinated phosphanes approach −30, much lower than expected.
- SMD and COSMO-RS methods showed good agreement, confirming the reliability of the results.
- The findings highlight the strong electronic effects of fluorination on phosphane basicity.

## Abstract

This study employed computational methods to investigate the basicity of a series of polyfluorinated phosphanes. Results revealed an exceptionally low basicity, with the computed pKaH values in acetonitrile approaching −30, a value significantly lower than anticipated. The good agreement between the SMD and COSMO-RS methods provided confidence in the reliability of these values. This unexpected behavior challenges conventional perceptions of phosphane basicity and deepens our understanding of the electronic effects of fluorination. The findings hold important implications for catalysis, ligand design, and main-group chemistry, where a precise comprehension of phosphane electronic properties is crucial. pKaH(MeCN) values, gas-phase basicities, and steric parameters are reported for 14 phosphanes.