SOLUBLE BISAXIALLY SUBSTITUTED (PHTHALOCYANINATO)RUTHENIUM COMPLEXES

Several attempts to prepare (tBu4Pc)Ru only led to an impure product (tBu4Pc)RuL(x). This reacts quantitatively with pyridine to form (tBu4Pc)Ru(py)2, easily purified by chromatography. In addition the preparation of (tBu4Pc)RuL2 with L = pyridine, 2-picoline (2-pic), 3-picoline (3-pic), 4-picoline (4-pic), 2,5-lutidine (2,5-lut), and 2,6-lutidine (2,6-lut), respectively, is described. All complexes are characterized by spectroscopic methods including H-1-NMR spectroscopy. Not even in the cases of (tBu4Pc)RuL2 with L = 2-pic and 2,5-lut, a careful removal of the ligands L by thermogravimetric methods (TG/DTA) leads to pure (tBu4Pc)Ru. For comparison, the bisadducts PcRuL2 with L = pyridine, picolines (2-pic, 3-pic, 4-pic), lutidines (2,3-lut, 2,5-lut, 2,6-lut), and chloropyridines (2-Clpy and 3-Clpy), respectively, are prepared by treatment of PcRu with an excess of the ligand. For the first time (phthalocyaninato)iron complexes PcFeL2 with sterically hindered axial ligands, e.g. PcFe(2-piC)2, are prepared and characterized by Fe-57 Mossbauer spectroscopy.