title: Cyanide-promoted demetalation of TrpyNiNCO: a route to sensitive metallotripyrrins of CoII, FeII, and MnII.
abstract: Etheral solutions of free base tripyrrins (HTrpy) were prepared by treatment of nickel isocyanate complexes (TrpyNiNCO) with excess cyanide. From these solutions sensitive metallotripyrrins with cobalt(II), iron(II), and manganese(II) ions (TrpyMX) and with a choice of external ligands X could be obtained in pure, crystalline form. Four cobalt and one iron chelate were characterized by X-ray crystallography. Tetracoordinate cobalt(II) species with X = I, NCO, and NCS displayed unstrained tetrahedral coordination geometries, whereas the pentacoordinate TrpyCoNO3 with the O,O-nitrato ligand narrows a trigonal bipyramidal coordination. TrpyFeNCO undergoes a redox-transformation to (TrpyFeNCO)2O upon crystallization and was structurally characterized as this with an almost linear Fe-O-Fe subunit. Donor association was studied by UV-vis spectroscopy employing different solvents and showed that TrpyMnX and TrpyFeX species are very prone to the formation of pentacoordinate species, whereas TrpyCoX compounds have an intermediate tendency to do so. Nevertheless, complex fragments of all three metal ions form 1D coordination polymers with dicyanamido ligands, which were investigated by means of IR and SQUID measurements.
authors.affiliation: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, 35032 Marburg, Germany. Martin.Broering@chemie.uni-marburg.de
authors.forename: Martin
authors.initials: M
authors.lastname: Bröring
authors.forename: Serguei
authors.initials: S
authors.lastname: Prikhodovski
authors.forename: Carsten D
authors.initials: CD
authors.lastname: Brandt
authors.forename: Esther Cónsul
authors.initials: EC
authors.lastname: Tejero
authors.forename: Silke
authors.initials: S
authors.lastname: Köhler
authors.forename: Clemens
authors.initials: C
authors.lastname: Pietzonka