Assessing the stereoelectronic properties of pyrrolyl phosphines and related ligands. The quantitative analysis of ligand effects (QALE)

Abstract

By application of the QALE model (quantitative analysis of ligand effects) to the standard reduction potentials (E° values) and the standard enthalpies of reduction (ΔH°) of the η-Cp(CO)(PZ3)Fe(COMe)+/0 couple (PZ3 = a phosphorus(III) ligand), and νCO for η-Cp(CO)(PZ3)Fe(COMe)0, we have determined that a minimum of four parameters are necessary to describe the stereoelectronic properties of the set of ligands PPhi(Pyr)3 − i (Pyr = pyrrolyl) and P(NC4H8)3 (NC4H8 = pyrrolidinyl). These parameters are χd, θ, Ear and the π acidity parameter, πp. The values of these parameters were determined by linear regression analysis of a set of QALE equations. The coefficients of these equations were based on the analyses of data for PR3, PPhiR3 − i, P(p-XC6H4)3, P(OR)3, and P(O-p-XC6H4)3. The parameters for P(Pyr)3 are χd = 31.9 ± 0.7, θ = 145 ± 3, Ear = 3.3 ± 0.2 and πp = 1.9 ± 0.2; and for P(NC4H8)3 the parameters are χd = −1.2 ± 1.4, θ = 145 ± 5, Ear = −0.6 ± 0.4 and πp = 0.9 ± 0.3. P(Pyr)3 is a poor σ donor that possesses an Ear parameter comparable to P(p-XC6H4)3 and a π acidity that is about two thirds that of P(OR)3 and half that of P(O-p-XC6H4)3. On the other hand, P(NC4H8)3, which is one of the strongest σ donor phosphorus(III) ligands, is a weak π acid with a value for Ear that is statistically indistinguishable from zero. PPhi(Pyr)3 − i and P(NC4H8)3 appear to be isosteric to P(p-XC6H4)3.