RUTHENIUM(II)-PHTHALOCYANINATES(1-) - SYN THESIS AND PROPERTIES OF (HALO)(CARBONYL)PHTHALOCYANINATO(1-)RUTHENINM(II)

Brown-violet (halo)(carbonyl)phthalocyaninato(1-)ruthenium(II), [Ru(X) (CO)Pc(-)] (X = Cl, Br) is prepared by oxidation of [Ru(X)(CO)Pc(2-)]( -) with the corresponding halogen or dibenzoylperoxide. The eff. magne tic moment mu(eff) = 1.74 (X = Cl), 1.68 mu(B) (Br) confirms the prese nce of a low-spin Ru-II complex of the Pc(-) radical. Accordingly, onl y the first ring oxidation at similar to 0.64 V and the first ring red uction at similar to-1.19V is observed in the cyclovoltammogram of [Ru (X)(CO)Pc(2-)](-). The UV-VIS-NIR spectra characterizing a monomeric P c(-) radical with intense pi-pi transitions at 14500, 19800, 25100 an d 33900 cm(-1) are compared with those of [Ru(Cl)(2)Pc(-)] and of mono meric as well as dimeric [Zn(Cl)Pc(-)]. The IR and resonance Raman(RR) spectra are characteristic for a Pc(-) radical, too. Diagnostic in-pl ane vibrations of the Pc(-) ligand are in the IR spectrum at 1071, 135 9, 1445 cm(-1) and in the RR spectrum (lambda(0) = 488.0 nm) at 567, 1 597 cm(-1). v(C-O) at 1950 cm(-1) and v(Ru-X) at 260 (X = Cl) resp. 18 4 cm(-1) (X = Br) are observed only in the IR spectrum.