RUTHENIUM(II) PHTHALOCYANINES - PREPARATI ON AND PROPERTIES OF DI(HALO)PHTHALOCYANINATORUTHENATE(II)

[Ru(Py)(2)Pc(2-)] reacts with molten ((n)Bu(4)N)X forming stable, gree n ((n)Bu(4)N)(2)[Ru(X)(2)Pc(2-)] (X = Cl, Br). The cyclovoltammogram s hows a quasireversible redoxprocess for the metal oxidation at E(1/2)( I) = -0.02 V (X = Cl) resp. 0.05 V (X = Br) and for the first ringoxid ation at E(1/2)(II) = 0.70 V. The typical pi-pi-transitions (B < Q < N) of the phthalocyanine dianion (Pc(2-)) are observed in the uv-vis s pectrum. With respect to Ru-III phthalocyanines B is shifted significa ntly to higher, Q, N to lower energy. The strong extra-band at 24.2 kK is diagnostic for these Ru-II phthalocyanines. The vibrational spectr a are typical for the Pc(2-) ligand with D-4h symmetry, too, and bands at 513, 909, 1171 und 1329 cm(-1) in the m.i.r. spectrum are specific for hexa-coordinated low spin Ru-II. In the Raman spectrum with excit ation at similar to 480 nm the intensity of the totally symmetrical Ru -X stretching vibration at 266 cm(-1) (X = Cl) resp. 168 cm(-1) (X = E r) together with a progression of up to three overtones is selectively resonance Raman enhanced. The asymmetrical Ru-X stretching vibration is observed in the f.i.r. spectrum at 272 cm(-1) (X = Cl) resp. 215 cm (-1) (X = Br).