IN-III PHTHALOCYANINES - SYNTHESIS, PROPE RTIES AND CRYSTAL-STRUCTUREOF M-CIS-DI(CYANATO(N))PHTHALOCYANINATO(2-)INDAT(III)

[In(Cl)Pc(2-)] reacts with bis(triphenylphosphine)iminium cyanate ((PN P)OCN) in dichloromethane to yield green-blue (b)(PNP)(cis)[In(NCO)(2) Pc(2-)] . CH2Cl2, which crystallizes in the triclinic space group P (1 ) over bar (No. 2) with Z = 2. The two cyanato(N) ligands are in a mut ually cis coordination (angle(N-NCO-In-N-NCO) = 84.2(3)degrees). The I n atom is displaced out of the plane of the four N-iso atoms towards t he two cyanato(N) ligands (d(In-Ct(N-iso)(4)) = 0.988 Angstrom). The a verage In-N-NCO and In-N-iso bond distances are 2.16(1) and 2.216(8) A ngstrom, respectively. The N-NCO-In-N-NCO moiety deviates by similar t o 4 degrees from the staggered conformation relative to the In(N-iso)( 4) sceleton. Though the cyanato(N) ligands are essentially linear, the re are different In-N-C angles (164.4(9) and 147.1(8)degrees) probably due to crystal packing effects. The pC(2-) ligand is distorted in an asymmetrically convex manner. The PNP cation adopts the bent conformat ion (angle(P-N(K)-P) = 143.5(6)degrees. 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). T he UV-VIS-NIR spectra and the vibrational spectra are discussed.