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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Disproportionation of O-Benzylhydroxylamine Catalyzed by a Ferric Bis- Picket Fence Porphyrin Complex
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Disproportionation of O-Benzylhydroxylamine Catalyzed by a Ferric Bis- Picket Fence Porphyrin Complex

机译：铁双栅栏栅卟啉配合物催化O-苄基羟胺歧化

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Hydroxylamine (NH_2OH) is an important molecule in biology that serves as an intermediate in the nitrogen cycle, and that can also be utilized as a nitric oxide donor in mammals under certain conditions. In light of this, the interaction of NH_2OH with hemes in proteins and model systems has gained much attention recently. In this study, we use the more stable, oxygen substituted O-benzylhydroxylamine (NH_2OBn) as a model for NH_2OH. Here, the reactivity of the ferric bis-picket fence porphyrin complexes [Fe(3,5-Me-BAFP)(ClO_4)] (1) and [Fe(3,5-Me-BAFP)(PF6)] (2) (3,5-Me-BAFP2- = dianion of tetra(2,6-bis(3,5-dimethylphenoxy)phenyl)porphyrin)) with NH_2OBn is investigated. The product of these reactions is characterized by UV/Vis and EPR spectroscopy and X-ray crystallography. We found that addition of excess NH_2OBn to our ferric porphyrin complexes results in reduction of the heme to the ferrous oxidation state. This is followed by disproportionation of additional NH_2OBn to yield the ferrous complex [Fe(3,5-Me-BAFP)(NH_3)_2] (3) as the final product. The crystal structure of (3) constitutes the first structural characterization of a bis-ammonia complex of a ferrous heme. The stability of this complex may be facilitated by the picket fences of the porphyrin ligand used here.
机译：羟胺（NH_2OH）是生物学中的重要分子，在氮循环中充当中间体，在某些条件下还可以用作哺乳动物的一氧化氮供体。鉴于此，近来NH 2 OH与血红素在蛋白质和模型系统中的相互作用受到了广泛关注。在这项研究中，我们使用更稳定的氧取代的O-苄基羟胺（NH_2OBn）作为NH_2OH的模型。在这里，铁双口袋栅栏卟啉配合物[Fe（3,5-Me-BAFP）（ClO_4）]（1）和[Fe（3,5-Me-BAFP）（PF6）]（2）的反应性研究了（3,5-Me-BAFP2- =四（2,6-双（3,5-二甲基苯氧基）苯基）卟啉的二价阴离子））与NH_2OBn。这些反应的产物通过UV / Vis和EPR光谱法和X射线晶体学表征。我们发现向我们的铁卟啉配合物中添加过量的NH_2OBn导致血红素还原为亚铁氧化态。这之后是歧化额外的NH_2OBn，以生成亚铁配合物[Fe（3,5-Me-BAFP）（NH_3）_2]（3）作为最终产物。 （3）的晶体结构构成亚铁血红素的双氨络合物的第一结构特征。该配合物的稳定性可通过此处使用的卟啉配体的栅栏来促进。

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