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Reaction of bis[phthalocyaninato(2-)iridium(II)] ([(Irpc 2- ) 2 ]) with nitric oxide in pyridine yields nitrosyl-containing intermediates that are immediately oxidized by air yielding pyri-dine-nitro-phthalocyaninato(2-)iridium(III) ([Ir(py)(NO 2 )pc 2- ]). Linear-bis(triphenylphos-phine)iminium trans-bisnitro-phthalocyaninatoiridate(III) ( 1 (PNP) trans [Ir(NO 2 ) 2 pc 2- ]) is prepared by air-oxidation of [(Irpc 2- ) 2 ] in dichloromethane in the presence of (PNP)NO 2 . It crystallizes in the triclinic space group P1̄ (no. 2) with the following cell parameters: a =10.649(1) Å, b = 12.357(1) Å, c = 12.841(1) Å, α = 75.47(1)°, β = 67.88(1)°, γ = 65.31(1)°, Z = 1. Ir III  is in the centre of a slightly waving pc 2-  ligand coordinating two nitro ligands in an eclipsed fram-arrangement. The average Ir-N iso  distance is 1.993(2) Å (N iso : isoindole N atom), the Ir-N distance is 2.189(3) Å (N: nitrite N atom), respectively. The structural data of the nitrite ion are: d(N-O) = 1.194(4) and 1.042(5) Å, ∠(O-N-O) = 131.7(4)°). Spectral properties with diagnostic IR absorption bands at 820, 1331 and 1398 cm -1  confirm the nitro coordination.

zeitschrift für naturforschung b

Synthese und Eigenschaften von trans-Bisnitro-phthalocyaninato(2-)iridat(III) und Pyridin-nitro-phthalocyaninato(2-)iridium(III); Kristallstruktur von linear- Bis(triphenylphosphin)iminium-trans-Bisnitro-phthalocyaninato(2-)iridat(III) / Synthesis and Properties of trans-Bisnitro-phthalocyaninato(2-)iridate(III) and Pyridine-nitro-phthalocyaninato(2-)iridium(III); Crystal Structure of linear- Bis(triphenylphosphine)iminium trans-Bisnitro-phthalocyaninato(2-)iridate(III)