Preparation and Characterization of Some Ruthenium(III) Porphyrins, Including the Crystal Structure of Bromo(octaethyl-porphinato)(triphenylphosphine) Ruthenium(III)
James, B.R., David Dolphin, Leung, T.W., Einstein, F.W.B., and Willis, A.C.
Can. J. Chem.
RuQLX and [RuQL2]X (H2Q = octaethylporphyrin (H2OEP) or tetraphenylporphyrin; L = PPh3, PBu3; X = Br, Cl) were prepared by oxidation of RuQL2 or RuQ(CO)L with the halogens or air in the presence of the hydrogen halides. The X = PF6 salts can be made with Et3O+PF6- as oxidant. Ru(II) porphyrin π-cation radical intermediates were sometimes detected. The x-ray crystal structure of Ru(OEP)(PPh3)Br reveals that Ru is displaced 0.049 Å from the plane of the pyrrole N atoms towards the phosphine. Ru(OEP)(py)Br and [Ru(OEP)(py)CH3CN]PF6 were prepared from Ru(OEP)(CO)py. The Ru(III) complexes are low-spin as shown by magnetic and ESR data. Optical and 1H NMR data, the latter showing large paramagnetic shifts, are also presented.