Darstellung und Eigenschaften der Phthalocyaninato(2–)metallate(I) von Cobalt,Rhodium und Iridium; Kristallstruktur von Tetra(n-butyl)ammoniumphthalocyaninato(2–)cobaltat(I)-Aceton-Solvat

Syntheses and Properties of Phthalocyaninato(2–)metallates(I) of Cobalt, Rhodium, and Iridium; Crystal Structure of Tetra(n-butyl)ammonium Phthalocyaninato(2–)cobaltate(I) Acetone Solvate Cobaltphthalocyaninate(2–) reacts with tetra(n-butyl)ammonium boranate in acetone yielding soluble tetra(n-butyl)ammonium phthalocyaninato(2–)cobaltate(I). The green platelets of its acetone solvate crystallize in the monoclinic space group P1 2₁/c (no. 14) with cell parameters: a = 12.370(1) Å, b = 23.370(3) Å, c = 15.952(8) Å, β = 93.55(2)°, Z = 4. The Co atom is located in the centre of the distorted phthalocyaninate (waving distortion). The average Co–N_iso distance is 1.894 Å. Dichlorophthalocyaninato(2–)metal(III) acid of rhodium and iridium reacts in boiling sodium isopropylate/isopropanol with tetra(n-butyl)ammonium boranate yielding violet tetra(n-butyl)ammonium phthalocyaninato(2–)rhodate(I) and -iridate(I). The UV-VIS-NIR spectra show normal π–π* transitions of the pc^2– ligand which are shifted in the series Co < Rh < Ir to higher energy. Absorbances (in 10³ cm^–1) at 18.2/19.4/21.4/23.6 (Co), 22.0/22.8/40.4 (Rh) and 25.6 (Ir) are assigned to M → pc^2– charge transfer transitions. The vibrational spectra are typical for the pc^2– ligand. The very low absorbance of the IR bands at 916/1067/1330 cm^–1 is diagnostic for low-valent metal phthalocyaninates.