Solution thermochemical study of a fluorous tertiary phosphine ligand in rhodium and ruthenium systems

The enthalpies of reaction of a fluorous tertiary phosphine, P(CH2CH2(CF2)(5)CF3)(3) (PRf3) with [Rh(CO)(2)Cl](2) (1) and Cp'Ru(COD)Cl (Cp' = eta(5)-C5H5 (2), eta(5)-C5Me5 (3)) leading to the formation of RhCl(CO)(PRf3)(2) and Cp'Ru(PRf3)(2)Cl complexes have been measured by anaerobic solution calorimetry in THF at 30.0 degrees C. These reactions are rapid and quantitative. The measured reaction enthalpies allow for a quantitative determination of characteristic phosphine steric and electronic parameters associated with this novel tertiary phosphine ligand. Sterically, the P(CH2CH2(CF2)(5)CF3)(3) ligand appears identical to PEt3.