Et4N[(CO)(CNBArF3)2Fe(H)(pdt)Ni(dcpe)] | 1448901-36-7

• 英文名称: Et4N[(CO)(CNBArF3)2Fe(H)(pdt)Ni(dcpe)]
• 英文别名: Et₄N[(CO)(CNBAr^F₃)2Fe(H)(pdt)Ni(dcpe)]
• CAS: 1448901-36-7
• 化学式: C₈H₂₀N*C₆₈H₅₅B₂F₃₀FeN₂NiOP₂S₂
• 分子量: 1878.64
• InChiKey: OUYDMXDZBFODTE-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

• 作为产物：
  描述：

  (CO)₂(CNBAr^F₃)₂Fe(pdt)Ni(dcpe) 、 四乙基氯化铵 、 氢气 在 十二/十四烷基二甲基氧化胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以28%的产率得到Et4N[(CO)(CNBArF3)2Fe(H)(pdt)Ni(dcpe)]
  参考文献：
  名称：

  Hydrogen Activation by Biomimetic [NiFe]-Hydrogenase Model Containing Protected Cyanide Cofactors

  摘要：

  Described are experiments demonstrating incorporation of cyanide cofactors and hydride substrate into [NiFe]-hydrogenase (H(2)ase) active site models. Complexes of the type (CO)(2)(CN)(2)Fe(pdt)Ni(dxpe) (dxpe = dppe, 1; dxpe = dcpe, 2) bind the Lewis acid B(C6F5)(3) (BAr3F) to give the adducts (CO)(2)(CNBAr3F)(2)Fe(pdt)Ni(dxpe), (1(BAr3F)(2), 2(BAr3F)(2)). Upon decarbonylation using amine oxides, these adducts react with H-2 to give hydrido derivatives [(CO)(CNBAr3F)(2)Fe(H)(pdt)Ni-(dxpe)](-) (dxpe = dppe, [H3(BAr3F)(2)](-); dxpe = dcpe, [H4(BAr3F)(2)](-)). Crystallographic analysis shows that Et4N[H3(BAr3F)(2)] generally resembles the active site of the enzyme in the reduced, hydride-containing states (Ni-C/R). The Fe-H center dot center dot center dot Ni center is unsymmetrical with r(Fe-H) = 1.51(3) angstrom and r(Ni-H) = 1.71(3) angstrom. Both crystallographic and F-19 NMR analyses show that the CNBAr3F- ligands occupy basal and apical sites. Unlike cationic Ni-Fe hydrides, [H3(BAr3F)(2)](-) and [H4(BAr3F)(2)](-) oxidize at mild potentials, near the Fc(+/0) couple. Electrochemical measurements indicate that in the presence of base, [H3(BAr3F)(2)](-) catalyzes the oxidation of H-2. NMR evidence indicates dihydrogen bonding between these anionic hydrides and R3NH+ salts, which is relevant to the mechanism of hydrogenogenesis. In the case of Et4N[H3(BAr3F)(2)], strong acids such as HCl induce H-2 release to give the chloride Et4N[(CO)(CNBAr3F)(2)Fe(Cl)(pdt)Ni-(dppe)].

  DOI：

  10.1021/ja404580r