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Zirconiumphthalocyanines: Synthesis and Properties of Chloride Ligated Phthalocyanines of Ter- and Quadrivalent Zirconium: Crystal Structure of cis-Di(triphenylphosphine)iminium-tri(chloro)phthalocyaninato(2-) zirconate(IV)-di(dichloromethane)
Gorsch, M.,Franken, A.,Sievertsen, S.,Homborg, H.
, (2008/10/08)
cis-Di(chloro)phthalocyaninato(2-)zirconium(IV) is obtained by the reaction of ZrCl4 with phthalodinitrile in 1-chloronaphthaline at 230°C. It reacts with molten di(triphenylphosphine)iminiumchloride ((PNP)Cl)yielding cis-di(triphenylphosphine)iminium-tri(chloro)phthalocyaninato( 2-)zirconate(IV), cis-(PNP)[ZrCl3Pc(2-)]. This crystallizes with two molecules of dichloromethane in the monoclinic space group P21/N with the lattice constants a=15.219(4) A, b=20.262(10) A, c=20.719(4) A, β=93.46(2)°, Z=4. The seven coordinated Zr atom is situated in a square base-trigonal cap polyhedron. The plane of the three chlorine atomsruns parallel to the plane of the four isoindole nitrogen atoms Niso. T he Zr-Cl distances range from 2.49 to 2.55 A, the Zr-Niso distances from2.26 to 2.29 A. Due to ion packing effects the Pc(2-) ligand shows an a symmetrical convex distortion. The PNP cation adopts the bent conformation. The P-N-P angle is 139°, the P-N distance 1.58 A. As confirmed by the cyclovoltammograms cis-(PNP)[ZrCl3Pc(2-)] is oxidized (anodically or chemically by Cl2) to yield cis-tri(chloro)phthalocyaninato(1-)zirconium(IV) and reduced (cathodically or chemically by [BH4](1-)) yielding chlorophthalocyaninato(2-)zirconium(III) and cis-di(triphenylphosphine)iminium-di(chloro)phthalocyaninato(2-)zirconate(III). The optical spectra show the typical π-π*-transitions of the Pc(2-) resp. Pc(1-) 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(1-) 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 vibrations as well as the asym. Zr-N stretching vibration of the [ZrCl(x)N4] skeleton (x=1-3) is assigned.
