- Structures and properties of octaethylporphinato(phenolate)iron(III) complexes with NH?O hydrogen bonds: Modulation of Fe-O bond character by the hydrogen bond
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Iron(III) porphinate complexes of phenolate that have NH?O hydrogen bonds on the coordinating oxygen were synthesized as models of heme catalase. The NH?O hydrogen bonds in the complexes lower an electron donation from the coordinating oxygen to iron and induce a long Fe-O bond and a positive redox potential. Iron(III) porphinate complexes of phenolate that have NH?O hydrogen bonds on the coordinating oxygen, [FeIII(OEP){O-2,6-(RCONH) 2C6H3}] (R = CF3 (1), CH3 (3)) and [FeIII(OEP)(O-2-RCONHC6H4)] (R = CF3 (2), CH3 (4)) (OEP = 2,3,7,8,12,13,17,18-octaethyl- 21H, 23H-porphinato), were synthesized and characterized as models of heme catalase. The presence of NH?O hydrogen bonds was established by their crystal structures and IR shifts of the amide NH band. The crystal structure of 1 shows an extremely elongated Fe-O bond, 1.926(3) ?, compared to 1.887(2) ? in 2 or 1.848(4) ? in [FeIII(OEP)(OPh)]. The NH?O hydrogen bond decreases an electron donation from oxygen to iron, resulting in a long Fe-O bond and a positive redox potential.
- Kanamori, Daisuke,Yamada, Yusuke,Onoda, Akira,Okamura, Taka-Aki,Adachi, Seiji,Yamamoto, Hitoshi,Ueyama, Norikazu
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p. 331 - 338
(2008/10/09)
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