Solution Thermochemical Study of Tertiary Phosphine Ligand Substitution Reactions in the RhCl(CO)(PR₃)₂System

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Abstract

The enthalpies of reaction of [Rh(CO)2Cl]2 (1) with a series of monodentate tertiary phosphine ligands, leading to the formation of RhCl(CO)(PR3)2 complexes, have been measured by anaerobic solution calorimetry in CH2Cl2 at 30.0 °C. These reactions are rapid and quantitative. The measured reaction enthalpies span a range of 43 kcal/mol. The relative stability scale established is as follows: P(NC4H4)3 < P(NC4H4)2(C6H5) < P(OPh)3 < P(p-CF3C6H4)3 < P(NC4H4)(C6H5)2 < P(p-ClC6H4)3 < AsEt3 < P(p-FC6H4)3 < PPh3 < P(p-CH3C6H4)3 < P(p-CH3OC6H4)3 < PPh2Me < P(OMe)3 < PPhMe2 < PEt3. The relative importance of phosphine electronic ligand parameters is closely examined in terms of the presented quantitative thermochemical information. Comparisons with enthalpy data in related organometallic systems are also presented.

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