(Si(o-C₆H₄P^iPr2)₃)Fe(Me) | 1240530-06-6

• 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: (Si(o-C₆H₄P^iPr2)₃)Fe(Me)
• 英文别名: (SiP^iPr₃)FeMe；(Si(o-C₆H₄PiPr₂))FeMe；Carbanide;iron(2+);tris[2-di(propan-2-yl)phosphanylphenyl]silanide
• CAS: 1240530-06-6
• 化学式: C₃₇H₅₇FeP₃Si
• 分子量: 678.713
• InChiKey: UYQQWCHKSHKGSD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.42
• 重原子数：
  42
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.49
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (Si(o-C₆H₄P^iPr2)₃)Fe(Me) 、 氢化氘 以 氘代苯 为溶剂， 反应 168.0h， 生成 (Si(o-C₆H₄P^iPr2)₃)Fe(D₂)(D)
  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：

  tris(2-(diisopropylphosphino)phenyl)silane 以 四氢呋喃 为溶剂， 生成 (Si(o-C₆H₄P^iPr2)₃)Fe(Me)
  参考文献：
  名称：

  单核 Fe(I) 和 Fe(II) 乙炔加合物及其还原质子化为末端 Fe(IV) 和 Fe(V) 卡宾

  摘要：

  固氮酶的活性可催化大气中的二氮转化为生物可利用的氨，最常通过将乙炔气还原为乙烯来测定。尽管乙炔作为底物具有实际重要性，但对其在富铁活性位点中的结合或激活知之甚少。非天然 C1 底物与高阶 C≥2 产物的“费托”型偶联也因固氮酶而闻名，尽管潜在的金属-碳多重键中间体仍未得到充分探索。在这里，我们报道了乙炔气体在单核三（膦基）甲硅烷基-铁中心（SiP3）Fe处的活化，得到Fe（I）和Fe（II）侧加合物，包括S = 1/2 FeI（η2） -HCCH）；后者通过脉冲 EPR 光谱和 DFT 计算来表征。这些化合物的还原质子化反应收敛于不寻常的、形式上的铁(IV)和铁(V)碳炔配合物的稳定例子，如反磁性(SiP3)Fe^CCH3和顺磁性阳离子S = 1/2 [(SiP3)Fe^ CCH3]+。两种烷基碳炔化合物都具有与锚定硅烷反式的短 Fe-C 三键（约 1.7 Å）。脉冲 EPR 实验、X 波段

  DOI：

  10.1021/jacs.9b06987

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.
• Silylation of Iron-Bound Carbon Monoxide Affords a Terminal Fe Carbyne
  作者：Yunho Lee、Jonas C. Peters

  DOI：10.1021/ja109678y

  日期：2011.3.30

  A series of monocarbonyl iron complexes in the formal oxidation states 0, +1, and +2 are accessible when supported by a tetradentate tris(phosphino)silyl ligand (SiPiPr 3 = [Si(o-C(6)H(4)PiPr(2))(3)](-)). X-ray diffraction (XRD) studies of these carbonyl complexes establish little geometrical change about the iron center as a function of oxidation state. It is possible to functionalize the terminal CO ligand of the most reduced carbonyl adduct by addition of SiMe3+ to afford a well-defined iron carbyne species, (SiP3iPr)Fe equivalent to C-OSiMe3. Single-crystal XRD data of this iron carbyne derivative reveal an unusually short Fe equivalent to C-OSiMe3 bond distance (1.671(2) angstrom) and a substantially elongated C-O distance (1.278(3) angstrom), consistent with Fe-C carbyne character. The overall trigonal bipyramidal geometry of (SiP3iPr)Fe equivalent to C-OSiMe3 compares well with that of the corresponding carbonyls, (SiP3iPr)Fe(CO)(-), (SiP3iPr)Fe(CO), and (SiP3iPr)Fe(CO)(+). Details regarding the electronic structure of the carbyne complex have been explored via the collection of comparative Mossbauer data for all of the complexes featured and also via DFT calculations. In sum, these data point to a strongly a-accepting Fischer-type carbyne ligand that confers stability to a low-valent iron(0) rather than high-valent iron(IV) center.