Abstract
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, CrIII or MnIII complexes, e.g. Cr(TTP)N3 or Mn(TTP)N3, yield Crv and Mnv complexes with terminal nitride ligands, e.g. Cr(TTP)N (1Ab) or Mn(TTP)N (1Bb) with concomitant liberation of 1 mol of N2. However, the FeIII complex Fe(TTP)N3 produces the mixed-valence ,μ-nitrido-bis[iron(III,IV)] complex, [Fe(TTP)]2N (1Cg) 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

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