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Structural characterization of verdoheme analogs : iron complexes of octaethyloxoporphyrin.
Autorzy
Rok wydania
1993
Czasopismo
Journal of the American Chemical Society
Numer woluminu
115
Strony
1422-1429
DOI
10.1021/ja00057a027
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
The verdohemes are shown to contain the planar, tetradentate oxoporphyrin structure. Structural studies of paramagnetic l(OEOP)FemCl2l, where is the monoanion of octaethyloxoporphyrin, by NMR spectroscopy and X-ray crystallography reveal that the iron is six-coordinate and high-spin (5 = 5/2). The iron resides in the plane of the oxoporphyrin and is coordinated by two equivalent axial chloride ligands. Paramagnetic |(OEOP)Fe"Cl| contains a five-coordinate iron which is also high-spin (5 = 2). The iron is 0.69 Á out of the porphyrin plane and bound to a single axial chloride. The average Fe-N distance increases from 1.964 Á in the iron(III) complex to 2.094 Á in the iron(II) complex. |(OEOP)FemCl2) was obtained by treatment of (OEP)Fe(py)2 (OEP is the dianion of octaethylporphyrin) with dioxygen in the presence of ascorbic acid to form the verdohemochrome [(OEOP)FeM(py)2]Cl, which was subsequently reacted with hydrogen chloride in air. Reduction of l(OEOP)FemCl2| with sodium dithionite yields air-sensitive |(OEOP)Fe"Cl). When |(OEOP)Fe"Cl| is dissolved in pyridine,[(OEOP)Fe"(py)2]Cl is reformed.
Adres publiczny
https://doi.org/10.1021/ja00057a027
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