PUB - Publikationen an der Universität Bielefeld

The reaction of the dimeric rhodium-complexes [(CpRhCl2)-Rh-x](2) (Cp-x = C5Me5, (C5 Bu2H3)-Bu-t) with silver oxalate Ag2C2O4 leads to polymeric species with the formula [(CpRh)-Rh-x(C2O4)](n) in high yields. These compounds react with Lewis-bases L [L = DMSO, P(OMe)(3), PPh3, P(C8H17)(3)] under depolymerisation to addition products of the type (CpRh)-Rh-x(C2O4)L. The solubility of these compounds depends on the ligand L. While Cp*Rh(C2O4)P(OMe)(3) is only soluble in polar organic solvents, Cp*Rh(C2O4)P(C8H17)(3) can be dissolved in unpolar solvents like alkanes. All these compounds are resistant against air and moisture. The structure of Cp*Rh(C2O4)P(OMe)(3) has been solved by X-ray analysis. UV-irradiation of Cp*Rh(C2O4)L (L = P(OMe)(3), PPh3) in CHX3 (X = Cl, Br) results in the elimination of CO2 and in the formation of the substitution products Cp*RhX2L.