Ruthenium(II) chemistry of phosphorus-based ligands, Ph 2PN(R)PPh 2 (R=Me or Ph) and Ph 2PN(Ph)P(E) Ph 2 (E=S or Se). Solution thermochemical study of ligand substitution reactions in the Cp′RuCl(COD) (Cp′=Cp, Cp*; COD=cyclooctadiene) system

Abstract

The enthalpies of reactions of Cp′RuCl(COD) (Cp′=Cp, Cp*; COD=cyclooctadiene) with bis(phosphino)amines of the type Ph 2PN(R)PPh 2(R=Me 1 or R=Ph 2) and the monochalcogen derivatives Ph 2PN(Ph)P(E)Ph 2(E=S 3 or Se 4) leading to the formation of Cp′RuCl(PNP) and Cp′RuCl{PNP(E)} complexes, respectively, have been measured by anaerobic solution calorimetry in THF at 30°C. These reactions are clean and quantitative. The synthesis and characterization of new organoruthenium complexes is reported. Comparisons with enthalpy data in this two related organoruthenium systems and other similar organometallic systems are also presented.