| Abstract: | Ruthenium(II)-Phthalocyaninates(1–): Synthesis and Properties of (Halo)(carbonyl)phthalocyaninato(1–)ruthenium(II) Brown-violet (halo)(carbonyl)phthalocyaninato(1–)ruthenium(II), Ru(X)(CO)Pc?] (X = Cl, Br) is prepared by oxidation of Ru(X)(CO)Pc2?]? with the corresponding halogen or dibenzoylperoxide. The eff. magnetic moment μeff = 1.74 (X = Cl), 1.68 μB (Br) confirms the presence of a low-spin RuII complex of the Pc? radical. Accordingly, only the first ring oxidation at ～0.64 V and the first ring reduction at ～ ?1.19 V is observed in the cyclovoltammogram of Ru(X)(CO)Pc2?]?. The UV-VIS-NIR spectra characterizing a monomeric Pc? radical with intense π-π* transitions at 14500, 19800, 25100 and 33900 cm?1 are compared with those of Ru(Cl)2Pc?] and of monomeric as well as dimeric Zn(Cl)Pc?]. The IR and resonance Raman(RR) spectra are characteristic for a Pc? radical, too. Diagnostic in-plane vibrations of the Pc? ligand are in the IR spectrum at 1071, 1359, 1445 cm?1 and in the RR spectrum (λ0 = 488.0 nm) at 567, 1597 cm?1. v(C? O) at 1950 cm?1 and v(Ru? X) at 260 (X = Cl) resp. 184 cm?1 (X = Br) are observed only in the IR spectrum. |
