Enthalpies of reaction of ruthenium complex Cp*Ru(COD)Cl (Cp* = .eta.5-C5Me5; COD = cyclooctadiene) with chelating tertiary phosphine ligands. Solution thermochemical investigation of ligand substitution and ring strain energies in Cp*Ru(PP)Cl complexes
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Abstract
The enthalpies of reaction of Cp*Ru(COD)Cl (Cp* = eta5-C5Me5: COD = cyclooctadiene) with a series of bidentate ligands, leading to the formation of Cp*Ru(PP)Cl complexes, have been measured by anaerobic solution calorimetry in THF at 30.0-degrees-C. The overall relative order of stability established for these complexes is as follows: dppm < arphos, dmpm, dppb < dppe, dppp, dppv < dmpe, depe. Comparisons of enthalpies of reaction with monodentate phosphine ligands afford a quantitative treatment of ring strain enthalpies in these organoruthenium metallacyclic compounds. The ring strain energies exhibited by four- and seven-membered metallacycles are on the order of 10 and 5 kcal/mol, respectively. Results of a single crystal X-ray diffraction study performed on one of the metallacyclic complexes, Cp*Ru(arphos)Cl, are reported. Comparisons with other metallacyclic complexes are also presented.
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