Abstract
The enthalpies of reaction of Rh(acac)(CO)2 (1) with a series monodentate tertiary phosphine ligands, leading to the formation of Rh(acac)(CO)(PR3) 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 12 kcal/mol. The relative stability scale established is as follows: PPh2(o-Tol) < P(p-CF3C6H4)3 ≈ P(p-ClC6H4)3 < P(p-FC6H4)3 < P(NC4H4)3 < P(NC4H4)2(C6H5) < P(m−CH3OC6H4)3 < P(NC4H4)(C6H5)2 < P(OPh)3 ≈ PPh2(p-Tol) ≈ P(m-Tol)3 < P(p−CH3C6H4)3 < PPh3 < P(p−CH3OC6H4)3 < PCy3 < PPh2Me < PiPr3 < PPhMe2. The relative importance of the phosphine stereoelectronic ligand parameters are examined in terms of the presented quantitative thermochemical information. Comparisons with enthalpy data in related organometallic systems are also presented.
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