bis(2-diisopropylphosphinophenyl)-chlorosilane | 1303610-08-3

• 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: bis(2-diisopropylphosphinophenyl)-chlorosilane
• 英文别名: bis(diisopropylphenylphosphino)chlorosilane；bis(o-diisopropylphosphinophenyl)-chlorosilane
• CAS: 1303610-08-3
• 化学式: C₂₄H₃₇ClP₂Si
• 分子量: 451.044
• InChiKey: ILISOJVUAWJWSJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.61
• 重原子数：
  28.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  bis(2-diisopropylphosphinophenyl)-chlorosilane 在 水 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 72.0h， 以68%的产率得到C₄₇H₇₃OP₅Si₂
  参考文献：
  名称：

  A 10⁶-Fold Enhancement in N₂-Binding Affinity of an Fe₂(μ-H)₂ Core upon Reduction to a Mixed-Valence Fe^IIFe^I State

  摘要：

  Transient hydride ligands bridging two or more iron centers purportedly accumulate on the iron-molybdenum cofactor (FeMoco) of nitrogenase, and their role in the reduction of N-2 to NH3 is unknown. One role of these ligands may be to facilitate N-2 coordination at an iron site of FeMoco. Herein, we consider this hypothesis and describe the preparation of a series of diiron complexes supported by two bridging hydride ligands. These compounds bind either one or two molecules of N-2 depending on the redox state of the Fe-2(mu-H)(2) unit. An unusual example of a mixed-valent Fe-II(mu-H)(2)Fe-I is described that displays a 10(6)-fold enhancement of N-2 binding affinity over its oxidized congener, quantified by spectroscopic and electrochemical techniques. Furthermore, these compounds show promise as function models of nitrogenase as substantial amounts of NH3 are produced upon exposure to proton and electron equivalents. The Fe(mu-H)Fe(N)(2) sub-structure featured herein was previously unknown. This subunit may be relevant to consider in nitrogenases during turnover.

  DOI：

  10.1021/ja507217v
• 作为产物：
  描述：

  (2-bromophenyl)diisopropylphosphine 在 正丁基锂 、 三氯硅烷 作用下， 以 乙醚 、 甲苯 为溶剂， 以97%的产率得到bis(2-diisopropylphosphinophenyl)-chlorosilane
  参考文献：
  名称：

  Dinitrogen Complexes of Sulfur-Ligated Iron

  摘要：

  We report a unique class of dinitrogen complexes of iron featuring sulfur donors in the ancillary ligand. The ligands utilized are related to the recently studied tris(phosphino)silyl ligands (2-R2PC6H4)(3)Si (R = Ph, iPr) but have one or two phosphine arms replaced with thioether donors. Depending on the number of phosphine arms replaced, both mononuclear and dinuclear iron complexes with dinitrogen are accessible. These complexes contribute to a desirable class of model complexes that possess both dinitrogen and sulfur ligands in the immediate iron coordination sphere.

  DOI：

  10.1021/ja2020907

文献信息

• An <i>S</i> = ¹/₂ Iron Complex Featuring N₂, Thiolate, and Hydride Ligands: Reductive Elimination of H₂ and Relevant Thermochemical Fe–H Parameters
  作者：Nina X. Gu、Paul H. Oyala、Jonas C. Peters

  DOI：10.1021/jacs.8b02603

  日期：2018.5.23

  strongly donating hydrides have been proposed to facilitate N2 binding to Fe and may also participate in the hydrogen evolution process concomitant to nitrogen fixation. Here, we report the synthesis and characterization of a thiolate-coordinated FeIII(H)(N2) complex, which releases H2 upon warming to yield an FeII-N2-FeII complex. Bimolecular reductive elimination of H2 from metal hydrides is pertinent

  相信在周转下会在 MoFe 固氮酶的 FeMo 辅因子 (FeMoco) 的 Fe 位点上积累，强烈捐赠的氢化物已被提议以促进 N2 与 Fe 结合，并且还可能参与伴随固氮的析氢过程。在这里，我们报告了硫醇盐配位的 FeIII(H)(N2) 复合物的合成和表征，该复合物在加热时释放 H2 以产生 FeII-N2-FeII 复合物。从金属氢化物双分子还原消除 H2 与酶和电催化剂的析氢过程有关，但明确定义的例子并不常见，通常从抗磁性的第二和第三行过渡金属中观察到。在这种氢化铁物质的 HER 上获得的动力学数据与双分子还原消除途径一致，
• Diiron Bridged-Thiolate Complexes That Bind N₂ at the Fe^IIFe^II, Fe^IIFe^I, and Fe^IFe^I Redox States
  作者：Sidney E. Creutz、Jonas C. Peters

  DOI：10.1021/jacs.5b04738

  日期：2015.6.17

  at least three oxidation states (Fe(II)Fe(II), Fe(II)Fe(I), and Fe(I)Fe(I)). The (N2-Fe(μ-SAr)Fe-N2) system undergoes reduction of the bound N2 to produce NH3 (∼50% yield) and can efficiently catalyze the disproportionation of N2H4 to NH3 and N2. The present scaffold also supports dinitrogen binding concomitant with hydride as a co-ligand. Synthetic model complexes of these types are desirable to ultimately

  所有已知的固氮酶辅因子都富含硫和铁，并被认为能够结合和还原 N2。尽管如此，结合 N2 并具有硫供体配体的过渡金属模型复合物的合成例子仍然很少。我们在此报告了一系列不同寻常的具有硫醇盐和二氮配体的低价二铁配合物。引入了一种新的双核配体支架，该支架支持 Fe(μ-SAr)Fe 二铁亚基，该亚基在至少三个氧化态 (Fe(II)Fe(II) 上协调二氮 (N2-Fe(μ-SAr)Fe-N2) 、Fe(II)Fe(I) 和 Fe(I)Fe(I))。(N2-Fe(μ-SAr)Fe-N2) 系统经过结合的 N2 还原生成 NH3（约 50% 的产率），并且可以有效地催化 N2H4 歧化为 NH3 和 N2。本支架还支持伴随氢化物作为共配体的二氮结合。