[PhBPCH2Cy3]FeCl | 919994-40-4

• 英文名称: [PhBPCH2Cy3]FeCl
• 英文别名: [PhBP^CH2Cy₃]FeCl；[PhB(CH2P(CH2Cy)2)3]FeCl
• CAS: 919994-40-4
• 化学式: C₅₁H₈₉BClFeP₃
• 分子量: 897.3
• InChiKey: PFQRJOCZEDTPOS-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [PhBPCH2Cy3]FeCl 在 sodium amalgam 作用下， 以 四氢呋喃 为溶剂， 生成 [PhB(CH2P(CH2Cy)2)3]Fe
  参考文献：
  名称：

  Fe(I)-Mediated Reductive Cleavage and Coupling of CO₂:  An Fe^II(μ-O,μ-CO)Fe^II Core

  摘要：

  THF solutions of a new iron(I) source, “[PhBPCH2Cy3]Fe” ([PhBPCH2Cy3] = [PhBP(CH2P(CH2Cy)2)3]−), effect the reductive cleavage of CO2 via O-atom transfer at ambient temperature. The dominant reaction pathway is bimetallic and leads to the formation of a structurally unprecedented diiron FeII(μ-O)(μ-CO)FeII core. X-ray data are also available to suggest that bimetallic reductive CO2 coupling to generate oxalate occurs as a minor reaction pathway. These initial observations forecast a diverse reaction landscape between CO2 and iron (I) synthons.

  DOI：

  10.1021/ja065524z
• 作为产物：
  描述：

  Tl[PhB(CH2P(CH2Cy)2)3] 、 iron(II) chloride 以 not given 为溶剂， 生成 [PhBPCH2Cy3]FeCl
  参考文献：
  名称：

  Fe(I)-Mediated Reductive Cleavage and Coupling of CO₂:  An Fe^II(μ-O,μ-CO)Fe^II Core

  摘要：

  THF solutions of a new iron(I) source, “[PhBPCH2Cy3]Fe” ([PhBPCH2Cy3] = [PhBP(CH2P(CH2Cy)2)3]−), effect the reductive cleavage of CO2 via O-atom transfer at ambient temperature. The dominant reaction pathway is bimetallic and leads to the formation of a structurally unprecedented diiron FeII(μ-O)(μ-CO)FeII core. X-ray data are also available to suggest that bimetallic reductive CO2 coupling to generate oxalate occurs as a minor reaction pathway. These initial observations forecast a diverse reaction landscape between CO2 and iron (I) synthons.

  DOI：

  10.1021/ja065524z

文献信息

• Spin-State Tuning at Pseudo-tetrahedral d⁶ Ions: Spin Crossover in [BP₃]Fe^II–X Complexes
  作者：Sidney E. Creutz、Jonas C. Peters

  DOI：10.1021/acs.inorgchem.6b00066

  日期：2016.4.18

  spectra, which allows for quantitative modeling of the thermodynamic parameters of the spin equilibria. These spin equilibria have also been studied by numerous techniques including paramagnetic nuclear magnetic resonance (NMR), infrared, and Mössbauer spectroscopies; X-ray crystallography; and solid-state superconducting quantum interference device (SQUID) magnetometry. These studies allow qualitative correlations

  发生自旋交叉的低配位过渡金属配合物仍然很少。我们在这里报告的一系列四配位的，伪四面体P 3种的Fe II由三支持-X复合物（膦）硼酸P 3（[PhBP 3 - [R ] - ）和phosphiniminato X型配体（-N═PR 3 '），结合起来可以调整系统的自旋交叉行为。大多数报道的铁配合物在接近或高于室温的温度下以溶液和固态经历自旋交叉。自旋态的变化与Fe和膦酰氨基配体的结合的N原子之间的π键键合度的显着变化一致。自旋交叉现象伴随着紫外-可见（UV-vis）吸收光谱的显着变化，这允许对自旋平衡的热力学参数进行定量建模。这些自旋平衡也已通过多种技术进行了研究，包括顺磁核磁共振（NMR），红外光谱和Mössbauer光谱学。X射线晶体学；固态超导量子干涉仪（SQUID）磁力计。
• CO2 reduction by Fe(i): solvent control of C–O cleavage versus C–C coupling
  作者：Caroline T. Saouma、Connie C. Lu、Michael W. Day、Jonas C. Peters

  DOI：10.1039/c3sc51262b

  日期：——

  distribution of the reaction of carbon dioxide with reactive iron(I) complexes supported by tris(phosphino)borate ligands, [PhBPR3]− ([PhBPR3]− = [PhB(CH2PR2)3]−; R = CH2Cy, Ph, iPr, mter; mter = 3,5-meta-terphenyl). Our studies reveal an interesting and unexpected role for the solvent medium with respect to the course of the CO2 activation reaction. For instance, exposure of methylcyclohexane (MeCy) solutions

  该手稿探讨了二氧化碳与负载有铁的活性铁（I）配合物反应的产物分布硼酸三（膦）酯配体，[PhBP - [R 3 ] -（[PhBP - [R 3 ] - = [值PhB（CH 2 PR 2）3 ] - ; R = CH 2 CY，PH，我PR，米之三;米叔= 3,5-元-三苯基）。我们的研究揭示了溶剂介质在CO 2活化反应过程中的有趣且出乎意料的作用。例如，曝光甲基环己烷到CO 2的（MeCy）溶液产生部分脱羰产物。当反应改为在苯或THF时，发生CO 2的还原偶联，生成桥联的草酸酯类物质。提出了旨在理解这种溶剂作用的反应研究，并表明产物的分布最终取决于溶剂协调铁中心的能力。当使用更多位阻于空间的辅助配体来支持铁（I）中心（即[PhBP Ph 3 ] -和[PhBP iPr 3 ] -）时，观察到完全脱羰可提供结构异常的二铁（II）产物[PhBP R 3 ] Fe} 2（μ-O）。甲机理假设
• XAS Characterization of a Nitridoiron(IV) Complex with a Very Short Fe−N Bond
  作者：Jan-Uwe Rohde、Theodore A. Betley、Timothy A. Jackson、Caroline T. Saouma、Jonas C. Peters、Lawrence Que

  DOI：10.1021/ic700818q

  日期：2007.7.1

  X-ray absorption spectroscopy has been used to characterize the novel nitridoiron(IV) units in two [PhBP3R]Fe(N) complexes (R = iPr and CyCH2) and obtain direct spectroscopic evidence for a very short Fe-N distance. The distance of 1.51-1.55 A reflects the presence of an FeN triple bond in accord with the observed FeN vibration observed for one of these species (nu(FeN) = 1034 cm(-1)). This highly covalent bonding interaction results in the appearance of an unusually intense pre-edge peak, whose estimated area of 100(20) units is much larger than those of the related tetrahedral complexes with Fe-I-N-2-Fe-I, Fe-II-NPh2, and Fe(III)NAd motifs, and those of recently described six-coordinate (FeN)-N-V and (FeN)-N-VI complexes. The observation that the Fe-IV-N distances of two [PhBP3R]Fe(N) complexes are shorter than the Fe-IV-O bond lengths of oxoiron(IV) complexes may be rationalized on the basis of the greater pi basicity of the nitrido ligand than the oxo ligand and a lower metal coordination number for the Fe(N) complex.
• Characterization of Structurally Unusual Diiron N_<i>x</i>H_<i>y</i> Complexes
  作者：Caroline T. Saouma、Peter Müller、Jonas C. Peters

  DOI：10.1021/ja903967z

  日期：2009.8.5

  A series of fascinating diiron complexes featuring bridging NxHy ligands stabilized by tris(phosphine)borate ([PhB(CH2PR2)(3)] = [PhBP3R]) ligands have been characterized. Hydrazine activation by [PhBP3R]Fe-Me (R = Ph or cyclohexylmethyl) leads to diiron Fe-2(mu-eta(1):eta(1)-N2H4) (mu-eta(2):eta(2)-N2H2) complexes featuring both bridging hydrazine and hydrazido ligands. Thermolysis of [PhBP23CHCy]Fe}(2)(mu-eta(1):eta(1)-N2H4) (mu-eta(2):eta(2)-N2H2) at 22 degrees C leads to a structurally unusual [PhBP2CHCy]Fe}(2)(mu-eta(1):eta(1)-N2H2)(mu-NH2)(2) complex featuring bridging HN=NH and NH2- ligands. This contrasts with [PhBP3Ph]Fe}(2)(mu-eta(1):eta(1)-N2H2)(mu-eta(2):eta(2)-N2H2), which can be chemically oxidized to produce either [PhBP3Ph]Fe}(2)(mu-eta(1):eta(1)-N2H2)(mu-eta(2):eta(2)-N2H2) or [PhBP3Ph]Fe}(2)(mu-NH)(2), depending on the conditions. The former product is the only known complex to contain bridging N2H2 ligands in each of their limiting states of oxidation (HN=NH vs HN-NH2-). The latter product constitutes the first example of a diiron Fe-2(mu-NH)(2) diamond-shaped core.