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Synthese von Bis[pyridin-phthalocyaninato(1,5-)iridium(II)]iodid und Pyridin-iodo-phthalocyaninato(2-)iridium(III)-Pyridin durch schrittweise Oxydation von Bis[pyridin-phthalocyaninato(2-)iridium(II)]/Synthesis of Bis[pyridine-phthalocyaninato(1,5-)iridium(II)] Iodide and Pyridine-iodo-phthalocyaninato(2-)iridium(III)-Pyridine by Successive Oxidation of Bis[pyridine-phthalocyaninato(2-)iridium(II)]

1997; De Gruyter; Volume: 52; Issue: 6 Linguagem: Inglês

10.1515/znb-1997-0610

1865-7117

H. Hückstädt, Heiner Homborg,

Metal-Catalyzed Oxygenation Mechanisms

Abstract Successive oxidation of bis[pyridine-phthalocyaninato(2-)iridium(II)] with iodine first yields mixed-valent bis[pyridine-phthalocyaninato(1,5-)iridium(II)] iodide ([(Ir(py)pc 1.5- } 2 ]I) and then pyridine-iodo-phthalocyaninato(2-)iridium(III)-pyridine ([Ir(py)(I)pc 2- ]·py). The latter crystallizes monoclinically with the following cell parameters: a = 10.258(1) Å, b = 17.589(3) Å, c = 19.723(2) Å, β = 92.95(1)°, space group P2 1 /n, Z = 4. Ir III is in the centre of a slightly distorted pc 2- ligand and coordinates pyridine and iodide in a trans-arrangement. The average Ir-N iso distance is 1.995(5) Å (N iso : isoindole N atom), the Ir-N py and Ir-I distan­ces are 2.102(5) and 2.657(1)Å, respectively. By a similar oxidation of [{Rh(py)pc 2- } 2 ] only [Rh(py)(I)pc 2- ]·py is obtained. Solid state spectral properties with diagnostic absorption bands at 1360. 1456, 5620 and 19800 cm -1 confirm the mixed-valent diphthalocyaninate(1.5-).