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The reaction of LFeCl 3  (L = N,N′,N″-trimethyl-1,4,7-triazacyclononane) with Na 2 SO 4 , Na 2 SO 3 /NaClO 4 , and Na 2 SeO 3 /NaClO 4  in aqueous solution affords the binuclear oxo bridged complexes [L 2 Fe 2 (μ-Ο)(μ-SΟ 4 ) 2 ]·3Η 2 Ο (1), [L 2 Fe 2 (μ-O)(μ-SO 3 ) 2 ]·5/3NaClO 4 ·(H 2 O) 3.67  (2), [L 2 Fe 2 (μ-O)(μ-SeO 3 ) 2 ](NaClO 4 ) 2.75 ·5H 2 O (3). The reaction of LFeCl 3  in dry methanol with Na 2 SO 4  yields yellow crystals of [L 2 Fe 2 (μ-SO 4 ) 3 ] · 2 H 2 O (4). The crystal structures of 1 and 2 have been determined by X-ray crystallography. Crystals of 1, 2, and 3 consist of neutral, binuclear μ-oxo bridged diiron(III) complexes which contain two additional O,O′-coordinated sulfato, sulfito, and selenito bridging ligands, respectively. The high spin ferric ions in 1, 2, and 3 are strongly intramolecularly antiferromagnetically spin exchange coupled with J values of —97(1), -104(2), and —104(2) cm -1  (H = —2JŜ,·Ŝ 2 , S 1  = S 2  = 5/2), respectively. 4 contains three μ-sulfato bridges between two Fe III  ions. Only a very weak antiferromagnetic coupling has been detected (J = —5.5(5) cm -1 ). Complex 1 serves as a model compound for the diiron(III) complex of the sulfate treated, oxidized form of the biomolecule uteroferrin.

zeitschrift für naturforschung b

Bioanorganische Modellkomplexe für Metalloproteine des Eisen(III): Synthese, Kristallstrukturen und Magnetismus der zweikernigen Komplexe [L 2 Fe 2  III (µ-O)(μ-SO 4 )2] · 3 H 2 O und [L 2 Fe 2  III (μ-O)(μ-SO 3 ) 2 ] · 5/3 NaClO 4  · (H 2 O) 3.67  (L = N,N′N″-Trimethyl-1,4,7-triazacyclononan) / Bioinorganic Model Complexes for Metalloproteins of Iron(III): Syntheses, Crystal Structures, and Magnetism of the Binuclear Complexes [L 2 Fe 2  III (μ-O)(μ-SO 4 ) 2 ]·3 Η 2 O and [L 2 Fe 2  III (μ-O)(μ-SO 3 )2] · 5/3 NaClO 4  · (H 2 O) 3 . 67  (L = N,N′,N″-Trimethyl-1,4,7-triazacyclononane)