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Metal Complexes with Tetrapyrrole Ligands XXXIII. Preparation of Azidochromium(III)-, Azidomanganese(III)-, and Azidoiron(III) Porphyrins and their Photolysis to Terminal or Bridged Nitridometal Porphyrins
Buchler, Johann Walter,Dreher, Christine
, p. 222 - 230 (2007/10/02)
Azidometal(III) porphyrins, e.g.M(TTP)N3 1 Aa - 1 Ca (M = Cr, Mn, Fe), are transformed into nitrido complexes on irradiation with ultraviolet light.Thus, Cr(III) or Mn(III) complexes, e.g.Cr(TTP)N3 or Mn(TTP)N3, yield Cr(V) and Mn(V) complexes with terminal nitride ligands, e.g.Cr(TTP)N (1 Ab) or Mn(TTP)N (1 Bb) with concomitant liberation of 1 mol of N2.However, the Fe(III) complex Fe(TTP)N3 produces the mixed-valence μ-nitrido-bis complex, 2N (1 Cg) and about 1.2 mol of N2 per mol of Fe.The azidometal(III) porphyrins are prepared from the corresponding hydroxo- or μ-oxo-metal(III) porphyrins and hydrazoic acid in benzene. - Key words: Chromium Porphyrins; Manganese Porphyrins; Nitridometal Complexes; Photolysis of Azido Complexes
