(CO)₂(CN)₂Fe(pdt)Ni(C₂H₄(P(C₆H₁₁)₂)₂) | 1448899-25-9

• 英文名称: (CO)₂(CN)₂Fe(pdt)Ni(C₂H₄(P(C₆H₁₁)₂)₂)
• 英文别名: (CO)₂(CN)₂Fe(pdt)Ni(dcpe)
• CAS: 1448899-25-9；1448901-52-7
• 化学式: C₃₃H₅₄FeN₂NiO₂P₂S₂
• 分子量: 751.42
• InChiKey: MAJAKRQBEHLXAA-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：

  三(五氟苯基)硼烷 、 (CO)₂(CN)₂Fe(pdt)Ni(C₂H₄(P(C₆H₁₁)₂)₂) 以 二氯甲烷 为溶剂， 以74%的产率得到(CO)₂(CNBAr^F₃)₂Fe(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
• 作为产物：
  描述：

  1,2-双(二环己基膦)乙烷氯化镍 、 dipotassium propane-1,3-dithiolate 、 Et4N[FeBr(CO)3(CN)2] 以 甲醇 、 乙腈 为溶剂， 反应 3.25h， 以45%的产率得到(CO)₂(CN)₂Fe(pdt)Ni(C₂H₄(P(C₆H₁₁)₂)₂)
  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