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In III -Phthalocyanine: Darstellung, Eigenschaften und Kristallstruktur von b-Bis(triphenylphosphin)iminium-cis-di(cyanato(N))phthalocyaninato- (2-)indat(III)/ In III Phthalocyanines: Synthesis, Properties and Crystal Structure of b-Bis(triphenylphosphine)iminium cis-Di(cyanato(N ))phthalocyaninato(2-)indate(III)

1996; De Gruyter; Volume: 51; Issue: 3 Linguagem: Inglês

10.1515/znb-1996-0305

1865-7117

Barbara Aβmann, A. Franken, Heiner Homborg,

Metal-Catalyzed Oxygenation Mechanisms

Abstract [In(Cl)Pc 2- ] reacts with bis(triphenylphosphine)iminium cyanate ((PNP)OCN) in dichloromethane to yield green-blue b (PNP) cis [In(NCO) 2 Pc 2- ] · CH 2 Cl 2 , which crystallizes in the triclinic space group P1̄ (No. 2) with Z = 2. The two cyanato(N) ligands are in a mutually cis coordination (∠ (N NCO -In -N NCO ) = 84.2(3)°). The In atom is displaced out of the plane of the four N iso atoms towards the two cyanato(N) ligands (d(In-Ct(N iso ) 4 ) = 0.988 Å). The average In-N NC0 and In-N iso bond distances are 2.16(1) and 2.216(8) Å, respectively. The N NCO -In -N NCO moiety deviates by ~ 4° from the staggered conformation relative to the In-(N iso ) 4 sceleton. Though the cyanato(N) ligands are essentially linear, there are different In-N -C angles (164.4(9) and 147.1(8)°) probably due to crystal packing effects. The Pc 2- ligand is distorted in an asymmetrically convex manner. The PNP cation adopts the bent conformation (∠(P-N(K)-P) = 143.5(6)°). The cyclic voltammogram shows three electrode processes, which are assigned to the redox pairs: Pc 3- /Pc 2- (-0.87 V) < In I /In III (-0.63 V) < Pc 2- /Pc - (0.69 V).The UV-VIS-NIR spectra and the vibrational spectra are discussed.