Structures and properties of octaethylporphinato(phenolate)iron(III) complexes with NH脙脙脙脙脙脙O hydrogen bonds: modulation of Fe脙脙脙脙脙脙O bond character by the hydrogen bond

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• 作者：Kanamori ; Daisuke ; Yamada ; Yusuke ; Onoda ; Akira ; Okamura ; Taka-aki ; Adachi ; Seiji ; Yamamoto ; Hitoshi ; et. al.
• 关键词：Hydrogen bond ; Phenolate complexes ; Porphyrin complexes ; Iron complexes ; Catalase ; X-ray analysis
• 刊名：Inorganica Chimica Acta
• 出版年：2005
• 期刊代码：40_00201693
• 类别：ch
• 出版时间：January 25, 2005
• 卷：358
• 期：2
• 页码：331-338
• 文件大小：387 K

摘要

Iron(III) porphinate complexes of phenolate that have NH芒芒芒O hydrogen bonds on the coordinating oxygen, [Fe^III(OEP){O-2,6-(RCONH)₂C₆H₃}] (R=CF₃ (1), CH₃ (3)) and [Fe^III(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芒芒芒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芒芒芒O bond, 1.926(3) 芒芒芒, compared to 1.887(2) 芒芒芒 in 2 or 1.848(4) 芒芒芒 in [Fe^III(OEP)(OPh)]. The NH芒芒芒O hydrogen bond decreases an electron donation from oxygen to iron, resulting in a long Fe芒芒芒O bond and a positive redox potential.