Oxo-phthalocyaninato-titan(IV) (PcTiO) shows weak electrical conductivity of 5 · 10~1 0 Ω" 1 cm" 1 at room temperature. Doping of PcTiO with I 2 is accompanied by an increase of conductivity up to 5· 10" 3 Ω" 1 cm" 1 . PcTiO was found to exist in two modifications built up by monomeric complexes: Phase I crystallizes monoclinic in the space group Ρ 2 l /c with the lattice constants a = 1341.1(6) pm, b = 1323.0(3) pm, c = 1381.0(4) pm, β = 103.72(3)°, Ζ = 4. Phase II forms a triclinic structure in space group PT and an unit cell of dimensions a = 1216.6(4)pm, b = 1258.4(5)pm, c = 864.1 (3)pm, α = 96.28(3)°, β = 95.03(4)°, y = 67.86(4)°, Ζ = 2. In both modifications the Ti-atom exhibits a square pyramidal coordination with a short Ti -Ο distance of 165 pm and 163 pm, respectively. Close contacts exist between the phthalocyaninato planes of neighbouring molecules. Einleitung Phthalocyaninato-Metallkomplexe (PcM), die mit axialen Brückenliganden zu linearen Ketten verknüpft sind, können Eigenschaften eindimensionaler, elektrischer Leiter aufweisen [2, 3], Beispiele dieser eindimensionalen Leiter sind (PcMC 2 ) x und (PcM pyz)^, in denen das Acetylidion (C|") oder Pyrazin (pyz) als Brückenliganden fungieren und das Zentralatom Μ ein * 14. Mitteilung über "Synthese und Eigenschaften neuartiger eindimensionaler Leiter". 13. Mitteilung siehe [1] * * Anschrift des Korrespondenzautors: Prof. Dr. J. Strähle,

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(Phthalocyaninato)iron(lI)-and -ruthenium(ll) Compounds with Isocyanides as Axial Ligands(Phthalocyaninato)iron(II) and -ruthenium(II) (PcM, M = Fe, Ru) react with aliphatic and aromatic monodentate isocyanides RNC (R = t-Bu, c-Hx, Bzl, Ph, Me2ph) with formation of the corresponding bisaxial substituted (phthalocyaninato)metal(II) compounds PCM(RNC)~ (M = Fe, Ru) 1 -5. The structures of these soluble compounds were determined by 'H and 13C NMR spectroscopy. The influence of the central metal atom M and of the organic group on the o-donorx-acceptor properties of the metal-ligand bond is investigated by IR spectroscopy. UV/VIS spectroscopy, TG/DTG/DTA measurements and FD mass spectroscopy additionally demonstrate the large differences when changing iron against ruthenium in 1-5. The thermal and mass spectroscopic differences point to the existence of pentacoordinated PcRu(I1) compounds.Isocyanide konnen sowohl mit Metallen in niedrigen als auch in normalen Oxidationsstufen in einer Vielfalt unterschiedlicher Bindungstypen stabile Komplexe bildenl).Im Rahmen unserer Untersuchungen uber eindimensionale Leiter, bei denen quadratisch planare Metallmacrocyclen uber zweizahnige, konjugationsfahige Bruckenliganden linear zu polymeren Ketten verkniipft werdenz), bot sich daher auch die Verwendung zweizahniger Isonitrile als Briickenligand an. Trotz der gegluckten Synthese einiger polymerer Systeme mit 1,4-Diisocyanbenzol als Brii~kenligand3~4) ist uber das Koordinationsverhalten von lsonitril-Liganden in den Polymeren nur wenig bekannt.Im Hinblick auf eine von uns postulierte Struktur-Leitfahigkeits-Abhangigkeit 2, ist die Untersuchung des Koordinationsverhaltens einzahniger Isocyanide an den von uns zur Polymerenbildung verwendeten Metallmacrocyclen von besonderem Interesse.Hierzu werden von uns erstmalig synthetisierte PcM(RNC),-Derivate (M = Fe, Ru) sowie einige literaturbekannte Systeme herangezogen 3, 5,6).

The synthesis and the properties of polymeric phthalocyaninatometal complexes of the type shown in figure 1 with Fe, Ru and Co as the central metal atom are described. TPPH2 and taaH2 are also used as macrocycles. In addition to pyrazine (pyz) and 1,4-diisocyanobenzene (dib) the cyano-group is used as a bridging ligand for the first time, such leading to µ-cyanophthalocyaninatocobalt (III) (10). 10 shows a conductivity of 10-2S.cm-1 (powder, compressed pellets) at room temperature without iodine-doping, the corresponding Fe and Mn polymers are also reported

(Phthalocyaninato)ruthenium(II) (I) was prepared by slow heating of (IIa) up to 330°C. (I) is reacted with various liquid or melted N‐donor ligands to yield monomeric derivatives (IIb) and (III).