Enthalpies of reaction of Cp′Ru(COD)Cl (Cp′ = C5H5, C5Me5; COD = cyclooctadiene) with P(p-XC6H4)3 (X = Cl, F, H, CH3, CF3, OCH3) ligands: Ligand steric vs electronic contributions to the enthalpy of reaction

Article abstract of DOI:10.1021/om00011a053

The enthalpies of reaction of Cp′Ru(COD)Cl (1; Cp′ = η⁵-C₅H₅, η⁵-C₅Me₅; COD = cyclooctadiene) with a series of para-substituted monodentate tertiary phosphine ligands, leading to the formation of Cp′Ru(PR₃)₂Cl, have been measured by anaerobic solution calorimetry in THF at 30.0°C. These reactions are rapid and quantitative. Structural studies have been carried out on three complexes in this series. The relative importance of phosphine steric vs electronic ligand parameters is more closely examined in terms of the presented quantitative thermochemical and structural information. Comparisons with enthalpy data in this and related organometallic systems are also presented.