RUTHENIUM(III) PHTHALOCYANINES - SYNTHESI S AND PROPERTIES OF DI(HALO)PHTHALOCYANINATO(1-)RUTHENIUM(III)

Di(halo)phthalocyaninato(1-)ruthenium(III), [Ru(X)(2)Pc(-)] (X = Cl, B r, I) is prepared by oxidation of [Ru(X)(2)Pc(2-)](-) (Cl, Br, OH) wit h halogene in dichloromethane. The magnetic moment of [Ru(X)(2)Pc(-)] is 2,48 mu(B), (X = Cl) resp. 2,56 mu(B), (X = Br) in accordance with a systeme of two independent spins (low spin Ru-III and Pc(-): S = 1/2 ). The optical spec tra of the red violet solution of [Ru(X)(2)Pc(-)] (Cl, Br) are typical for the Pc(-) ligand with the ''B'' at 13.5 kK, ' 'Q(1)'' at 19.3 kK and ''Q(2) region'' at 31.9 kK. Sytematic spectral changes within the iron group are discussed. The presence of the Pc(-) ligand is confirmed by the vibrational spectra, too. Characteristic a re the metal dependent bands in the m.i.r. spectra at 1352 and 1458 cm (-1) and the strong Raman line at 1600 cm(-1). The antisymmetric Ru-X stretch (nu(as)(Ru-X)) is observed at 189 cm(-1) (X = I) resp. 234 cm( -1) (X = Br). There are two interdependent bands at 295 and 327 cm(-1) in the region expected for nu(as)(Ru-Cl) attributed to strong interac tion of nu(as)(Ru-Cl) with an out-of-plane Pc(-) tilting mode of the s ame irreducible representation. Only the symmetric Ru-Br stretch at 18 3 cm-L is selectively enhanced in the resonance-Raman(RR) spectra. The Raman line at 168 cm(-1) of the diiodo complex is assigned to loosely bound iodine. The broad band at 978 cm(-1) in the RR spectra of the d ichloro complex is due to an intraconfigurational transition within th e electronic ground state of low spin Ru-III split by spin orbit coupl ing.