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首页> 外文期刊>Chemistry: A European journal >Synthesis and Reactivity of Mononuclear Iron Models of [Fe]- Hydrogenase that Contain an Acylmethylpyridinol Ligand
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Synthesis and Reactivity of Mononuclear Iron Models of [Fe]- Hydrogenase that Contain an Acylmethylpyridinol Ligand

机译：含酰基甲基吡啶醇配体的[Fe]-加氢酶的单核铁模型的合成和反应性

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摘要

[Fe]-hydrogenase has a single iron-containing active site that features an acylmethylpyridinol ligand. This unique ligand environment had yet to be reproduced in synthetic models; however the synthesis and reactivity of a new class of small molecule mimics of [Fe]-hydrogenase in which a mono-iron center is ligated by an acylmethylpyridinol ligand has now been achieved. Key to the preparation of these model compounds is the successful C-O cleavage of an alkyl ether moiety to form the desired pyridinol ligand. Reaction of solvated complex [(2-CH_2CO-6-HOC_5H_3N)Fe(CO)_(2~-) (CH_3CN)_2]~+(BF_4)~- with thiols or thiophenols in the presence of NEt3 yielded 5-coordinate iron thiolate complexes. Further derivation produced complexes [(2-CH_2CO-6- HOC_5H_3N)Fe(CO)_2(SCH_2CH_2OH)] and [(2-CH_2CO-6- HOC_5H_3N)Fe(CO)_2(CH_3COO)], which can be regarded as models of FeGP cofactors of [Fe]-hydrogenase extracted by 2-mercaptoethanol and acetic acid, respectively. When the derivative complexes were treated with HBF_4?Et_2O, the solvated complex was regenerated by protonation of the thiolate ligands. The reactivity of several models with CO, isocyanide, cyanide, and H_2 was also investigated.
机译：[Fe]-加氢酶具有单个含铁的活性位点，该活性位点具有酰基甲基吡啶吡啶配体。这种独特的配体环境尚未在合成模型中复制。然而，现在已经实现了新型的[Fe]-加氢酶小分子模拟物的合成和反应性，其中单铁中心被酰基甲基吡啶醇配体连接。制备这些模型化合物的关键是烷基醚部分的成功C-O裂解，以形成所需的吡啶醇配体。在NEt3存在下，溶剂化的络合物[（2-CH_2CO-6-HOC_5H_3N）Fe（CO）_（2〜-）（CH_3CN）_2] +（BF_4）〜-与硫醇或硫酚的反应生成5价铁硫醇盐配合物。进一步推导产生了络合物[（2-CH_2CO-6- HOC_5H_3N）Fe（CO）_2（SCH_2CH_2OH）]和[（2-CH_2CO-6-HOC_5H_3N）Fe（CO）_2（CH_3COO）]，可以将其视为模型2-巯基乙醇和乙酸分别提取[Fe]-加氢酶的FeGP辅助因子。当用HBF_4→Et_2O处理衍生物配合物时，通过硫醇盐配体的质子化作用再生了溶剂化的配合物。还研究了几种模型与CO，异氰化物，氰化物和H_2的反应性。

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