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Monomeric and dimeric iron(III) complexes of 5-hydroxy-10,15,20-triphenylporphyrin: formation of cyano and pyridine complexes of (5-oxo-10,15,20-triphenylphlorin)iron.
Autorzy
Rok wydania
2002
Czasopismo
European Journal of Inorganic Chemistry
Strony
1806-1815
DOI
10.1002/1099-0682(200207)2002:7<1806::AID-EJIC1806>3.0.CO;2-%23
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
The reaction of [(TrPP)FeII(py)2] (TrPP = dianion of 5,10,15‐triphenylporphyrin) with hydrogen peroxide results in oxygenation of the (porphyrin)iron and the formation of (10,15,20‐triphenyl‐5‐oxophlorin)iron [(5‐O‐TrPP)Fe(py)2]. Coupled oxidation of [(TrPP)FeIIICl] in the presence of ascorbic acid and potassium cyanide in methanol leads to oxidative hydroxylation of the porphyrin ring to form a cyclic dimer [(5‐O‐TrPP)FeIII]2. Three out of four pyrrole 1H NMR resonances of the dimeric complex present the characteristic displacement with respect to the typical position for the high‐spin (tetraphenylporphyrin)iron(III) complexes. The linewidths of the β‐H pyrrole resonances correlate with specific locations of the respective protons within the dimeric structure. Addition of HCl to [(5‐O‐TrPP)FeIII]2 results in cleavage of the dimer producing [(5‐OH‐TrPP)FeIIICl]. [(5‐O‐TrPP)FeIII]2 is also split with acetic anhydride to give (5‐acetoxy‐10,15,20‐triphenylporphyrin)iron(III). In the presence of [D5]pyridine or a large excess of cyanide ion, [(5‐O‐TrPP)FeIII]2 undergoes cleavage to form air‐sensitive [(5‐O‐TrPP)Fe(py)2] or [(5‐O‐TrPP)Fe(CN)2]2−. The pyrrole pattern observed for [(5‐O‐TrPP)Fe(py)2] is similar to that determined on the basis of an analysis carried out for four (oxophlorin)iron regioisomers obtained from hemes. For comparison, the characteristic 1H NMR features of the typical (5‐substituted‐10,15,20‐triphenylporphyrin)iron(III) complexes have been investigated for the series of high‐spin and low‐spin complexes. The spin‐density distribution in the (oxophlorin)iron skeleton is dominated by the radical‐like electronic structure. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)
Adres publiczny
https://doi.org/10.1002/1099-0682(200207)2002:7<1806::AID-EJIC1806>3.0.CO;2-%23
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