Phosphine EB and CB Values

作者：Russell S. Drago, Steven Joerg · 发表于：Journal of the American Chemical Society · 年份：1996 · DOI：10.1021/ja953581e · 被引用次数：60 · 研究领域：Chemical Reaction Mechanisms、Asymmetric Hydrogenation and Catalysis、Organometallic Complex Synthesis and Catalysis

This article presents a scale of σ donor strengths for phosphines. The phosphine parameters, E B and C B, can be used in combination with previously reported parameters for oxygen, nitrogen, and sulfur donors to measure σ-basicity. The advantages of combining donors from more than one family to analyze reactivity are demonstrated. When substituents are changed in a family of donors, the change in the C B / E B ratio is small and this is shown to lead to limitations in the conclusions that can be drawn from substituent constant correlations. QALE analyses also treat only single families and are subject to the same limitations. The dual parameter E B, C B basicity scale is less reliant upon steric effects than QALE analyses to rationalize trends in the reactivity of phosphines. This leads to an alternative interpretation of a large body of phosphine chemistry. A model is presented to support the idea that the π-acceptor properties of the phosphines decrease regularly as their σ basicity increases. It is shown that the phosphine σ donor, E B and C B parameters inappropriately can correlate reactivity toward acceptors that π-back-bond when a data set involves only phosphines. In order to obtain reliable acceptor parameters and to detect a π-back-bond component in donor−acceptor interactions, donors from families other than phosphines have to be studied with the π-donor.