Metallkomplexe mit Tetrapyrrol‐Liganden, III. Darstellung von Metallkomplexen des Octaäthylporphins aus Metall‐acetylacetonaten

Abstract

Die Metall-acetylacetonate M(acac)z (M = Mg, Co, Ni, Cu, Zn), M(acac)3 (M = Al, Sc, V, Cr, Mo, Mn, Fe, Co, In, Ce), MO(acac)2 (M = Ti, V), MoOz(acac)z und M(acac)4 (M = Zr, Th) werden mit Octaathylporphin [ l ; (OAP)Hz] umgesetzt (Tabb. 1 und 2). Abgesehen von Komplexen der Metalle Ce und Th werden die Octathylporphin-Chelate 2-5 (Tab. 3) erhalten. Als gunstigstes Losungsmittel fur die Umsetzungen hat sich Phenol erwiesen : diesem ist Imidazol nur im Falle des Sc(acac)3 wegen der Saurelabilitat der bisher nicht beschriebenen Scandiumkomplexe 3g und 5 uberlegen. Aus Mo(acac), wird Octaathylporphinatomolybdan(1V)-oxid [4c; (OAP)MoO] gewonnen. Ausgehend von Zr(acac)4 erhalt man Octaathylporphinato-zirkon-diacetat [2 i ; (OAP)Zr(OAc)z]. Metal Complexes with Tetrapyrrole Ligands, III l a ) . Preparation of Metal Complexes of Octaethylporphin from Metal Acetylacetonates Octaethylporphin [l; (OAP)Hz] is treated (tables 1 and 2) with the metal acetylacetonates M(acac)z (M = Mg, Co, Ni, Cu, Zn), M(acac)3 (M = Al, Sc, V, Cr, Mo, Mn, Fe, Co, In, Ce), MO(acac)z (M = Ti, V), MoOz(acac)z and M(acac)4 (M = Zr, Th). With the exception of Ce-and Th-complexes the metalloporphyrins 2-5 have been obtained (table 3). Phenol has been found to be the best solvent for the reactions described. Only in the case of Sc(acac)3, imidazole is more useful because the hitherto unreported scandium complexes 3g and 5 are very labile towards acids. Mo(acac)3 yields octaethylporphinato-molybdenum(1v)-oxide [4c ;(OAP)MoO]. Starting from Zr(acac)4, octaethylporphinato-zirconium-diacetate [2i;(OAP)Zr(OAc)z] is obtained.

(Tetraphenylporphyrinato)hafnium(IV) Diacetate Acetonitrile Solvate

“…The extent of this doming for the title compound can be seen from the out-of-plane displacement of the 24-atom porphyrin core. The related diacetate derivatives [(OEP)Zr(OAc)2] and [(OEP)Hf(OAc)2] (OEP is 2, 3,7,8,12,13,17,18-octaethylporphyrinato) also exhibit similar geometric features, with eight-coordinate metal centers, bidentate cis-acetate ligands and domed porphyrin cores (Buchler et al, 1971;Hoard, 1975 (Brand & Amold, 1993), [(TPP)ZrC12].thf (Kim, Whang, Kim & Do, 1993) and [(OEP)Zr(CH2SiMe3)2] (Brand & Arnold, 1992), where Tol is toluene and thf is tetrahydrofuran. All of the zirconium and hafnium porphyrins were shown to have cis coordination of ligands, with the metal positioned above the N4 porphyrin plane.…”

Metallkomplexe mit Tetrapyrrol-Liganden, XXXI [1]. Neutrale und anionoide Bisporphinate des Gers und Praseodyms / Metal Complexes with Tetrapyrrole Ligands, XXXI [1]. Neutral and Anionoid Bisporphinates of Cerium and Praeseodymium

“…Seltenerdmetall-Porphinate [2 b] wurden erst zugänglich, als Horrocks (Jr.) [10a-f] und dann Srivastava [11] unsere Erfahrungen in der Verwendung von Metallacetylacetonaten zum Einbau von Sc 111 , Zr IV und Hf IV in Porphyrine [12] Wie schon früher an LuH(Pc)2 und GdH(Pc)2 beobachtet [6,8], kann man 2 gemäß Gl. (3) deprotonieren, wobei ein Sandwich-Anion entsteht.…”

Highly Selective and Green Oxidation of Sulfides with Urea Hydrogen Peroxide in the Presence of Mn(III) Porphyrin Supported onto Carbon Nanotubes

“…meso-Tetrakis(4-hydroxyphenyl)porphyrin (H 2 THPP), and meso-tetrakis(4-hydroxyphenyl)-porphyrinatomanganese(III) acetate (MnTHPPOAc) were prepared according to the literature. [23,24] MnTHPPOAc has been supported on the functionalized multi-wall carbon nanotubes (MnTHPPOAc@ MWCNT) according to the reported procedure. [14,25] General heterogeneous oxidation procedure.…”