pKaH values and θH angles of phosphanes to predict their electronic and steric parameters

Abstract

Phosphanes play an important role in various applications, serving as a class of organic bases with basicities spanning more than 30 orders of magnitude. Accessing comprehensive basicity data for phosphanes has been challenging due to scattered information across multiple sources and notable gaps in the existing data. In this report, we present basicities (pK_aH values) of a diverse set of phosphanes, both newly measured or calculated and collected from the literature. We demonstrate that pK_aH values can serve as an alternative to Tolman electronic parameters (TEP values) in evaluating the electronic properties of phosphanes. Additionally, we suggest parameters for assessing the steric properties of phosphanes without the need for preparation or calculation of metal-ligand complexes.