[(μ-SeCH2)2NH]Fe2(CO)6 | 1313861-42-5

• 英文名称: [(μ-SeCH2)2NH]Fe2(CO)6
• 英文别名: [Fe₂{μ(SeCH₂)₂NH}(CO)₆]
• CAS: 1313861-42-5
• 化学式: C₈H₅Fe₂NO₆Se₂
• 分子量: 480.745
• InChiKey: DKKCCONBFFTALZ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [(μ-SeCH2)2NH]Fe2(CO)6 、 氰化四乙基铵 以 乙腈 为溶剂， 反应 3.0h， 以65%的产率得到[Fe₂{μ(SeCH₂)₂NH}(CO)₄(CN)₂](N(Et)₄)₂
  参考文献：
  名称：

  [FeFe]-加氢酶的[2Fe]簇中硫属元素化物的取代保留了较高的酶促活性†

  摘要：

  [FeFe] -Hydrogenases有效地催化了H 2的吸收和释放，这是由于存在无机[6Fe-6S]-辅因子（H-簇）而引起的。该辅助因子由[4Fe–4S]簇与独特的[2Fe]簇耦合而成，在该簇中发生H 2 / H +的催化转化。我们在本文中报道了硒取代的[2Fe]团簇[Fe 2 {μ（SeCH 2）2 NH}（CO）4（CN）2 ] 2-（ADSe）的合成及其在体外成功整合到天然蛋白质中的过程[FEFE] -hydrogenases HydA1从支架莱茵衣藻和CPI从巴氏梭菌产生完全活性的酶（HydA1-ADSe和CpI-ADSe）。FT-IR光谱和X射线结构分析证实了活性位点存在结构完整的ADSe。电化学分析表明，含硒的酶比天然酶更倾向于产氢。与以前的硫族化物交换研究相反，本文的S到Se交换不是基于使用离子簇成分的简单重构方法，而是基于预先合成的含硒[2Fe]模拟物的体外成熟。生物

  DOI：

  10.1039/c7dt03785f
• 作为产物：
  描述：

  [Fe₂{μ(SeCH₂)₂N(Cbz)}(CO)₆] 在 BF₃*OEt₂ 、 EtSH 作用下， 以 二氯甲烷 为溶剂， 以31%的产率得到[(μ-SeCH2)2NH]Fe2(CO)6
  参考文献：
  名称：

  Synthesis and Characterization of Single, Double, and Triple Butterfly [2Fe2E] (E = Se, S) Cluster Complexes Related to the Active Site of [FeFe]-Hydrogenases

  摘要：

  As the active site mimics of [FeFe]-hydrogenases, 14 new butterfly [2Fe2E] (E = Se, S) cluster complexes have been prepared by various synthetic routes. The N-substituted single-butterfly [2Fe2Se] complexes [(mu-SeCH2)(2)NC(O)R]Fe-2-(CO)(6) (1, R = Me; 2, R = Ph; 3, R = PhCH2O) were prepared by reactions of the in situ formed (mu-LiSe)(2)Fe-2(CO)(6) with RC(O)N(CH2Cl)(2), whereas the corresponding [2Fe2S] complexes {(mu-SCH2)(2)NC6H4R-P]Fe-2(CO)(6) (4, R = CO2Et; 5, R = CH2OH) were produced by reaction of the in situ generated (mu-HS)(2)Fe-2(CO)(6) with aqueous CH2O followed by treatment with p-RC6H4NH2. The parent single-butterfly [2Fe2Se] complex [(mu-SeCH2)(2)NH]Fe-2(CO)(6) (6) could be prepared by reaction of the N-substituted complex 3 with deprotecting reagent BBr3, BF3 center dot OEt2/EtSH, or BF3 center dot OEt2/Me2S, whereas the N-substituted single-butterfly [2Fe2Se] complexes [(mu-SeCH2)(2)NC(O)R]Fe-2(CO)(6) (7, R = Et; 8, R = PhCH2) were produced by reactions of 6 with acylating agents RC(O)Cl in the presence of Et3N. While the known parent single-butterfly [2Fe2S] complex [(mu-SCH2)(2)NH]Fe-2(CO)(6) reacted with 2,6-[ClC(O)](2)C5H3N to afford double-butterfly [2Fe2S] complex [Fe-2(CO)(6)(mu-SCH2)(2)NC(O)](2)(2,6-C5H3N) (9), the new N-hydroxyethyl-substituted single-butterfly [2Fe2Se] complex [(mu-SeCH2)(2)N-(CH2)(2)OH]Fe-2(CO)(6) (10) could be obtained by the in situ reaction of (mu-HSe)(2)Fe-2(CO)(6) with (HOCH2)(2)N(CH2)(2)OH. Interestingly, complex 10 could react with [ClC(O)](2)CH2 or 1,3,5-[ClC(O)](3)C6H3 in the presence of Et3N to give the corresponding double-butterfly [2Fe2Se] complex [Fe-2(CO)(6)(mu-SeCH2)(2)N(CH2)(2)O2C](2)CH2 (11) and triple- butterfly complex [Fe-2(CO)(6)(mu-SeCH2)(2)N(CH2)(2)O2C](3)(1,3,5-C6H3) (12), whereas the known single-butterfly [2Fe2S] complex [(mu-SCH2)(2)N-(CH2)(2)OH]Fe-2(CO)(6) could react with 2,6-[ClC(O)](2)C5H3N and 1,3,5-[ClC(O)](3)C6H3 in the presence of Et3N to afford the corresponding double-butterfly [2Fe2S] complex [Fe-2(CO)(6)(mu-SCH2)(2)N(CH2)(2)O2C](2)(2,6-C5H3N) (13) and triple-butterfly complex [Fe-2(CO)(6)(mu-SCH2)(2)N(CH2)(2)O2C](3)(1,3,5-C6H3) (14), respectively.All the new complexes 1-14 have been characterized by elemental analysis and spectroscopy, as well as by X-ray crystallography for 1-4, 7-9 and 14. In addition, the electrochemical study indicated that complexes 1 and 2 can catalyze the Proton reduction of HOAc to give hydrogen.

  DOI：

  10.1021/om200395g