Abstract
The enthalpies of reaction of Cp‘Ru(COD)Cl (Cp‘ = C5H5, C5Me5; COD = 1,5- cyclooctadiene) with a series of π-acceptor bidentate phosphines, leading to the formation of Cp‘Ru(PP)Cl complexes, have been measured by anaerobic calorimetry in THF at 30 °C. These reactions are rapid and quantitative. Structural studies have been carried out on two complexes in this series. The overall relative order of stability established for these complexes in both Cp and Cp* systems is (PhO)2PNMeNMeP(OPh)2 > Ph2PNMeNMeP Ph2 ≈ (C4H4N)2PCH2CH2P(NC4H4)2 > ((EtO2C)2C4H2N)2PCH2CH2P(NC4H2(CO2 Et)2)2. Present thermochemical data are discussed in terms of the nature of the bonding involved in the present complexes.
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