Synthese und Eigenschaften von Bis(tetra(n-butyl)ammonium)-μ-carbidodi(halogenophthalocyaninato(2–)ferraten(IV)); Kristallstruktur von Bis(tetra(n-butyl)ammonium)-μ-carbidodi(fluorophthalocyaninato(2–)ferrat(IV))-Trihydrat

✍ Scribed by Arne Kienast; Heiner Homborg

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: German
• Weight: 253 KB
• Volume: 624
• Category: Article
• ISSN: 0372-7874
• DOI: 10.1002/(sici)1521-3749(199801)624:1<107::aid-zaac107>3.0.co;2-q

✦ Synopsis

Inhaltsu È bersicht. l-Carbido-di(pyridinphthalocyaninato(2±)eisen(IV)) reagiert mit Tetra(n-butyl)ammoniumhalogenid ( n Bu 4 N)X) in Lo È sung (X = F) oder in einer Schmelze (X = Cl, Br) zu Bis(tetra(n-butyl)ammonium-l-carbidodi(halogenophthalocyaninato(2±)ferrat(IV)). Das Fluoro-Komplexsalz kristallisiert als Trihydrat monoklin in der Raumgruppe P12 1 /n1 mit den Zellparametern: a = 15,814(1) A Ê ; b = 22,690(5) A Ê ; c = 25,127(3) A Ê ; b = 98,27(1)°; Z = 4. Die Fe-Atome befinden sich fast im Zentrum (Ct) der (N iso ) 4 -Ebenen (d(Fe±Ct) = 0,053(1) A Ê ; N iso : Isoindol-N-Atom). Der mittlere (Fe±N iso )-Abstand betra È gt 1,939(4) A Ê , der (Fe±(l-C))-Abstand 1,687(4) A Ê und der (Fe±F)-Abstand 2,033(2) A Ê . Das (Fe±(l-C)±Fe)-Geru È st ist linear (179,5(3)°). Die beiden pc 2± -Liganden sind in einer Staffel-Konformation (u = 42(1)°) einander zugeneigt (konvexe Verzerrung). Die asymmetrische (Fe±(l-C)±Fe)-Valenzschwingung (in cm ±1 ) liegt im IR-Spektrum bei 917 (X = F), 918 (Cl) sowie 920 (Br), die symmetrische dagegen im Resonanz-Raman-Spektrum bei 476 cm ±1 . Die IR-aktive asymmetrische (Fe± X)-Valenzschwingung (in cm ±1 ) beobachtet man bei 336 (X = F), 203 (Cl) bzw. 182 (Br).

Synthesis and Properties of Bis(tetra(n-butyl)ammonium)l-Carbido-di(halophthalocyaninato(2±)ferrates(IV)); Crystal Structure of Bis(tetra(n-butyl)ammonium) l-Carbido-di(fluorophthalocyaninato(2±)ferrate(IV)) Trihydrate Abstract.

l-Carbido-di(pyridinephthalocyaninato(2±)iron(IV)) reacts with tetra(n-butyl)ammonium halide ( n Bu 4 N)X) in solution (X = F) or in a melt (X = Cl, Br) to yield bis(tetra(n-butyl)ammonium l-carbido-di(halophthalocyaninato(2±)ferrat(IV)). The fluoro-complex salt crystallizes as a trihydrate monoclinically in the space group P12 1 /n1 with the following cell parameters: a = 15.814(1) A Ê ; b = 22.690(5) A Ê ; c = 25.127(3) A Ê ; b = 98.27(1)°, Z = 4. The Fe atoms are almost in the centre (Ct) of the (N iso ) 4 planes (N iso : isoindoline-N atom) with a Fe±Ct distance of 0.053(1) A Ê . The average Fe±N iso distance is 1.939(4) A Ê , the Fe±(l-C) distance 1.687(4) A Ê and the Fe±F distance 2.033(2) A Ê . The Fe±(l-C)±Fe core is linear (179.5(3)°). The pc 2 -ligands are staggered (u = 42(1)°) with a convex distortion. The asymmetric Fe±(l-C)±Fe stretch (in cm ±1 ) is observed in the IR spectra at 917 (X = F), 918 (Cl) and 920 (Br) and the symmetric Fe±(l-C)±Fe stretch at 476 cm ±1 in the resonance Raman spectra. The IR active asymmetric Fe±X stretch (in cm ±1 ) absorbs at 336 (X = F), 203 (Cl), 182 (Br), respectively.