Darstellung und spektroskopische Charakterisierung von Di(acido)phthalocyaninatorhodaten(III)

Preparation and Spectroscopical Characterization of Di(acido)phthalocyaninatorhodates(III) Triethylendiaminorhodiumiodide reacts quickly and completely with boiling phthalodinitrile precipitating ?rhodiumphthalocyanine”?, which is purified and dissolved in alkaline media as di(hydroxo)phthalocyaninatorhodate(III). Acidification in the presence of halides or pseudohalides yields less soluble acidophthalocyaninatorhodium reacting with tetra-n-butyl-ammonium(pseudo)halide to give (blue)green tetra-n-butyl-ammoniumdi(acido)phthalocyaninatorhodate(III), (ⁿBu₄N)[Rh(X)₂Pc^2?] (X = Cl, Br, I, N₃, CN, NCO, SCN, SeCN). The asym. Rh? X-stretching vibration (v_as(RhX)) is observed in the f.i.r. at 290 (X = Cl), 233 (Br), 205 (I), 366 (N₃), 347 (CN), 351 (NCO), 257 (SCN) and 214 cm^?1 (SeCN). v_s(RhI) is the only sym. Rh? X-stretching vibration excited at 131 cm^?1 in the Raman spectrum. The m.i.r. and resonance Raman spectra are typical for hexacoordinated phthalocyaninatometalates(III). The influence of the axial ligands is very small. The frequency of the stretching vibrations of the pseudohalo-ligands are as expected (in the case of the ambident ligands the bonding atom is named first): v_as(NN) at 2006 and v_s(NN) at 1270 cm^?1 (N₃); v_as(CN) at 2126 (CN), 2153 (NCO), 2110 (SCN) and 2116 cm^?1 (SeCN). The characteristic π–π*-transitions of the Pc^2?-ligand dominate the UV-vis spectra. The splitting of the Q and N region is discussed and the weak absorbance at ca. 22 kK is assigned to a n–π*-transition.