ZIRCONIUMPHTHALOCYANINES - SYNTHESIS AND PROPERTIES OF CHLORIDE LIGATED PHTHALOCYANINES OF TERVALENT AND QUADRIVALENT ZIRCONIUM CRYSTAL-STRUCTURE OF CIS-DI(TRIPHENYLPHOSPHINE)IMINIUM-TRI(CHLORO)PHTHALOCYANINATO(2-)ZIRCONATE(IV)-DI(DICHLOROMETHANE)

cis-Di(chloro)phthalocyaninato(2-)zirconium(IV) is obtained by the reaction of ZrCl4 with phthalodinitrile in 1-chloronaphthaline at 230 degrees C. It reacts with molten di(triphenylphosphine)iminiumchloride ((PNP)Cl) yielding cis-di(triphenylphosphine)iminium-tri(chloro)phthalocyaninato(2-)zirconate(IV), cis-(PNP)[ZrCl(3)Pc(2-)]. This crystallizes with two molecules of dichloromethane in the monoclinic space group P2(1)/n with the lattice constants a = 15.219(4) Angstrom, b = 20.262(10) Angstrom, c = 20.719(4) Angstrom, beta = 93.46(2)degrees, Z = 4. The seven coordinated Zr atom is situated in a ''square base-trigonal cap'' polyhedron. The plane of the three chlorine atoms runs parallel to the plane of the four isoindole nitrogen atoms N-iso. The Zr-Cl distances range from 2.49 to 2.55 Angstrom, the Zr-N-iso distances from 2.26 to 2.29 Angstrom. Due to ion packing effects the Pc(2-) ligand shows an asymmetrical convex distortion. The PNP cation adopts the bent conformation. The P-N-P angle is 139 degrees, the P-N distance 1.58 Angstrom. As confirmed by the cyclovoltammograms cis-(PNP)[ZrCl(3)Pc(2-)] is oxidized (anodically or chemically by Cl-2) to yield cis-tri(chloro)phthalocyaninato(1-)zirconium(IV) and reduced (cathodically or chemically by [BH4](-)) yielding chlorophthalocyaninato(2-)zirconium(III) and cis-di(triphenylphosphine)iminium-di(chloro)phthalocyaninato(2 -)zirconate(III). The optical spectra show the typical pi - pi*-transitions of the Pc(2-) resp. Pc(-) ligand not much affected by the different states of oxidation and coordination of zirconium. The same is true for the vibrational spectra of the Pc(2-) resp. Pc(-) ligand. In the f.i.r. spectra between 350 and 150 cm(-1) the asym. and sym. Zr-Cl stretching and Cl-Zr-Cl deformation vibration as well as the asym. Zr-N stretching vibration of the [ZrClxN4] skeleton (x = 1-3) is assigned.