Diiron Oxadithiolate Type Models for the Active Site of Iron-Only Hydrogenases and Biomimetic Hydrogen Evolution Catalyzed by Fe2(μ-SCH2OCH2S-μ)(CO)6
Diiron Oxadithiolate Type Models for the Active Site of Iron-Only Hydrogenases and Biomimetic Hydrogen Evolution Catalyzed by Fe2(μ-SCH2OCH2S-μ)(CO)6
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DOI：
10.1021/om0507373
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发表时间：
2005-11
期刊：
影响因子：
2.8
通讯作者：
Li-Cheng Song;Zhi-Yong Yang;Hongzhu Bian;Yang Liu;Hu-Ting Wang;Xu‐Feng Liu;Q. Hu
中科院分区：
文献类型：
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作者：
Li-Cheng Song;Zhi-Yong Yang;Hongzhu Bian;Yang Liu;Hu-Ting Wang;Xu‐Feng Liu;Q. Hu
本文系统地研究了单、双含恶二硫代二铁模型化合物对唯铁氢化酶活性中心的仿生化学作用。最简单的模型是Fe_2（μ-SCH_2OCH_2S-μ）（CO）_6（1），它是由（μ-S_2）Fe_2（CO）_6与2当量的Et_3BHLi反应，然后用过量的（ClCH_2）_2O直接处理或在Et_3N存在下用2当量的CF_3CO_2H和过量的（ClCH_2）_2O连续处理而制得的。1与1当量Me 3 NO在MeCN中在室温下进一步反应，随后处理中间体Fe 2（μ-SCH2OCH2S-μ）（CO）5L（L = MeCN或Me 3 N）与1当量Et 4 NCN、PPh 3或Cp（CO）2FeSPh反应得到单一模型Fe 2（μ-SCH2OCH2S-μ）（CO）5La（2）La =（CN）（Et4N）; 4，Cp（CO）2FeSPh）的产率为62 - 93%，而中间体Fe 2（μ-SCH_2OCH_2S-μ）（CO）_5L与0.5当量的1，4-（CN）_2C_6H_4、（η_5-Ph_2PC_5H_4）_2Fe（dppf）或（η_5-Ph_2PC_5H_4）_2Ru（dppr）反应，得到了[Fe_2（μ-SCH_2OCH_2S-μ）（CO）_5]_2Lb（5，Lb = 1，4-（CN）_2C_6H_4; 6，dppf; 7，dppr）的双模型化合物[Fe_2（μ-SCH_2OCH_2S-μ）（CO）_5]_2Lb（5，Lb = 1，4-（CN）_2C_6H_4; 6，dppf; 7，dppr）。
The biomimetic chemistry of single and double oxadithiolatodiiron-containing model compounds for the active site of Fe-only hydrogenases (FeHases) has been systematically studied. The simplest such model, Fe2(μ-SCH2OCH2S-μ)(CO)6 (1), was prepared by reaction of (μ-S2)Fe2(CO)6 with 2 equiv of Et3BHLi followed by direct treatment with excess (ClCH2)2O or by successive treatment with 2 equiv of CF3CO2H and excess (ClCH2)2O in the presence of Et3N. Further reaction of 1 with 1 equiv of Me3NO in MeCN at room temperature followed by treatment of the intermediate Fe2(μ-SCH2OCH2S-μ)(CO)5L (L = MeCN or Me3N) with 1 equiv of Et4NCN, PPh3, or Cp(CO)2FeSPh gave the single models Fe2(μ-SCH2OCH2S-μ)(CO)5La (2, La = (CN)(Et4N); 3, PPh3; 4, Cp(CO)2FeSPh) in 62−93% yields, whereas the in situ treatment of the intermediate Fe2(μ-SCH2OCH2S-μ)(CO)5L with 0.5 equiv of 1,4-(CN)2C6H4, (η5-Ph2PC5H4)2Fe (dppf), or (η5-Ph2PC5H4)2Ru (dppr) afforded the double models [Fe2(μ-SCH2OCH2S-μ)(CO)5]2Lb (5, Lb = 1,4-(CN)2C6H4; 6, dppf; 7, d...