ZIRCONIUMPHTHALOCYANINES - SYNTHESIS AND PROPERTIES OF CHLORIDE LIGATED PHTHALOCYANINES OF TERVALENT AND QUADRIVALENT ZIRCONIUM CRYSTAL-STRUCTURE OF HALOCYANINATO(2-)ZIRCONATE(IV)-DI(DICHLOROMETHANE)

cis-Di(chloro)phthalocyaninato(2-)zirconium(IV) is obtained by the rea ction of ZrCl4 with phthalodinitrile in 1-chloronaphthaline at 230 deg rees C. It reacts with molten di(triphenylphosphine)iminiumchloride (( PNP)Cl) yielding nium-tri(chloro)phthalocyaninato(2-)zirconate(IV), ci s-(PNP)[ZrCl(3)Pc(2-)]. This crystallizes with two molecules of dichlo romethane in the monoclinic space group P2(1)/n with the lattice const ants a = 15.219(4) Angstrom, b = 20.262(10) Angstrom, c = 20.719(4) An gstrom, beta = 93.46(2)degrees, Z = 4. The seven coordinated Zr atom i s situated in a ''square base-trigonal cap'' polyhedron. The plane of the three chlorine atoms runs parallel to the plane of the four isoind ole 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 io n packing effects the Pc(2-) ligand shows an asymmetrical convex disto rtion. 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 cycl ovoltammograms cis-(PNP)[ZrCl(3)Pc(2-)] is oxidized (anodically or che mically by Cl-2) to yield cis-tri(chloro)phthalocyaninato(1-)zirconium (IV) and reduced (cathodically or chemically by [BH4](-)) yielding chl orophthalocyaninato(2-)zirconium(III) and enylphosphine)iminium-di(chl oro)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 zir conium. The same is true for the vibrational spectra of the Pc(2-) res p. 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.