dinitrogenhydrido(tris(2-(diisopropylphosphino)phenyl)silyl)iron(II) | 1338002-13-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: dinitrogenhydrido(tris(2-(diisopropylphosphino)phenyl)silyl)iron(II)
• 英文别名: (Si(o-C₆H₄P^iPr2)₃)Fe(N₂)(H)；(Si(o-C₆H₄PiPr₂))Fe(N₂)(H)；(SiP^iPr₃)Fe(N₂)(H)
• CAS: 1338002-13-3
• 化学式: C₃₆H₅₅FeN₂P₃Si
• 分子量: 692.7
• InChiKey: PKFBUQVHCHVENT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：

  一氧化碳 、 dinitrogenhydrido(tris(2-(diisopropylphosphino)phenyl)silyl)iron(II) 生成 (Si(o-C6H4PiPr2)3)Fe(CO)(H)
  参考文献：
  名称：

  铁金属硼烷的杂解氢裂解和催化加氢

  摘要：

  H 2在铁硼烷中的铁-硼键上的可逆、异裂加成以及正式的氢化物转移到硼上得到铁-硼氢化物-氢化物复合物。这些化合物催化烯烃和炔烃氢化成相应的烷烃。值得注意的是，硼能够充当将氢化物转移到基材的穿梭机。在金属实验室和相关系统中跨金属-硼键的异溶底物添加以及金属-配体双功能催化的背景下，结果很有趣。

  DOI：

  10.1021/om400281v
• 作为产物：
  描述：

  dihydrogen(tris(2-(diisopropylphosphino)phenyl)silyl)iron(II) tetrakis(2,5-bis(trifluoromethyl)phenyl)borate 、 氮 在 ethyldiisopropylamine 作用下， 以 not given 为溶剂， 生成 dinitrogenhydrido(tris(2-(diisopropylphosphino)phenyl)silyl)iron(II)
  参考文献：
  名称：

  A Nonclassical Dihydrogen Adduct of S = ¹/₂ Fe(I)

  摘要：

  We have exploited the capacity of the "(SiP3iPr)Fe(I)" scaffold to accommodate additional axial ligands and characterized the mononuclear S = 1/2 H-2 adduct complex (SiP3iPr)Fe-I(H-2). EPR and ENDOR data, in the context of X-ray structural results, revealed that this complex provides a highly unusual example of an open-shell metal complex that binds dihydrogen as a ligand. The H2 ligand at 2 K dynamically reorients within the ligand-binding pocket, tunneling among the energy minima created by strong interactions with the three Fe-P bonds.

  DOI：

  10.1021/ja207003m

文献信息

• Hydricity of an Fe–H Species and Catalytic CO₂ Hydrogenation
  作者：Henry Fong、Jonas C. Peters

  DOI：10.1021/ic502508p

  日期：2015.6.1

  Despite renewed interest in carbon dioxide (CO2) reduction chemistry, examples of homogeneous iron catalysts that hydrogenate CO2 are limited compared to their noble-metal counterparts. Knowledge of the thermodynamic properties of iron hydride complexes, including M-H hydricities (Delta GH(-)), could aid in the development of new iron-based catalysts. Here we present the experimentally determined hydricity of an iron hydride complex: (SiP(iPr)(3))Fe(H-2)(H), Delta GH(-)) = 54.3 +/- 0.9 kcal/mol [SiP(iPr)(3) = [Si(o-C(6)H(4)PiPr(2))(3)](-)]. We also explore the CO2 hydrogenation chemistry of a series of triphosphinoiron complexes, each with a distinct apical unit on the ligand chelate (Si-, C-, PhB-, N, B). The silyliron (SiP(R)(3))Fe (R = iPr and Ph) and boratoiron (PhBP3iPr)Fe (PhBP3ipr = [PhB(CH(2)PiPr(2))(3)](-)) systems, as well as the recently reported (CP3iPr)Fe (CP3iPr = [C(o-C(6)H(4)PiPr(2))(3)](-)), are also catalysts for CO2 hydrogenation in methanol and in the presence of triethylamine, generating methylformate and triethylammonium formate at up to 200 TON using (SiP3Ph)FeCl as the precatalyst. Under stoichiometric conditions, the iron hydride complexes of this series react with CO2 to give formate complexes. Finally, the proposed mechanism of the (SiP3iPr)-Fe system proceeds through a monohydride intermediate (SiP3iPr)Fe(H-2)(H), in contrast to that of the known and highly active tetraphosphinoiron, (tetraphos)Fe (tetraphos = P(o-C6H4PPh2)(3)), CO2 hydrogenation catalyst.