{[PhBP3iPr]}FeCl | 579444-62-5

• 英文名称: {[PhBP3iPr]}FeCl
• 英文别名: {[PhBP₃^iPr]}FeCl；[PhBP₃^iPr]FeCl；[tris(diisopropylphosphino)borate]FeCl；[iron(II)(phenyl)5B(CH2P(iPr)2)3Cl]
• CAS: 579444-62-5
• 化学式: C₂₇H₅₃BClFeP₃
• 分子量: 572.75
• InChiKey: SWXAAUNUUGIFDT-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：

  {[PhBP3iPr]}FeCl 以 四氢呋喃 为溶剂， 生成 [PhBP₃^iPr]Fe(NPEt₃)
  参考文献：
  名称：

  四面体协调的 L3Fe-Nx 平台，可容纳末端氮化物 (FeIV⋮N) 和二氮 (FeI-N2-FeI) 配体

  摘要：

  描述了一个四面体协调的 L3Fe-Nx 平台，可容纳终端氮化物 (L3FeIVN) 和二氮 (L3FeI-N2-FeIL3) 功能。已通过多核 NMR（1H、31P 和 15N）和红外光谱在环境条件下的溶液中表征了具有抗磁性的 L3FeIVN 物种。标题复合体的电子结构也已使用 DFT 进行了探索。末端氮化物复合物氧化偶合生成先前报道的 L3FeI-N2-FeIL3 物质。该反应构成由两个铁中心介导的六电子转换。氮化物配合物的还原质子化释放出 NH3 作为重要的反应产物。

  DOI：

  10.1021/ja048713v
• 作为产物：
  描述：

  lithium,methanidyl-di(propan-2-yl)phosphane 在 TMEDA 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成 {[PhBP3iPr]}FeCl
  参考文献：
  名称：

  The Strong-Field Tripodal Phosphine Donor, [PhB(CH₂PⁱPr₂)₃]^-, Provides Access to Electronically and Coordinatively Unsaturated Transition Metal Complexes

  摘要：

  This paper introduces a sterically encumbered, strong-field tris(diisopropylphosphino)borate ligand, [PhBp(3)(iPr)] ([PhBP3iPr] = [PhB((CH2PPr2)-Pr-i)(3)](-)), to probe aspects of its conformational and electronic characteristics within a host of complexes. To this end, the TI(I) complex, [PhBP3iPr]TI (1), was synthesized and characterized in the solid-state by X-ray diffraction analysis. This precursor proves to be an effective transmetallating agent, as evidenced by its reaction with the divalent halides FeCl2 and CoX2 (X = Cl, 1) to produce the monomeric, 4-coordinate, high-spin derivatives [PhBP3iPr]FeCl (2) and [PhBP3iPr]CoX (X = Cl (3), 1 (4)) in good yield. Complexes 2-4 were each characterized by X-ray diffraction analysis and shown to be monomeric in the solid-state. For conformational and electronic comparison within a system exhibiting higher than 4-coordination, the 16-electron ruthenium complexes {[PhBP3iPr]Ru(mu-Cl)}(2) (5) and {[PhBP3]Ru(mu-Cl)}(2) (6) were prepared and characterized ([PhBP3] = [PhB(CH2PPh2)(3)](-)). The chloride complexes 2 and 3 reacted with excess CO to afford the divalent, monocarbonyl adducts [PhBP3iPr]- FeCl(CO) (7) and [PhBP3iPr]CoCl(CO) (8), respectively. Reaction of 4 with excess CO resulted in the monovalent, dicarbonyl product [PhBP3iPr]Co-I(CO)(2) (9). Complexes 5 and 6 also bound CO readily, providing the octahedral, 18-electron complexes [PhBP3iPr]RuCl(CO)(2) (10) and [PhBP3]RuCl(CO)(2) (11), respectively. Dimers 5 and 6 were broken up by reaction with trimethylphosphine to produce the mono-PMe3 adducts [PhBP3iPr]RuCl(PMe3) (12) and [PhBP3]RuCl(PMe3) (13). Stoichiometric oxidation of 3 with dioxygen provided the 4-electron oxidation product [PhB(CH2P(O)Pr-i(2))(2)((CH2PPr2)-Pr-i)]CoCl (14), while exposure of 3 to excess oxygen results in the 6-electron oxidation product [PhB(CH2P(O)Pr-i(2))(3)]CoCl (15). Complexes 2 and 4 were characterized via cyclic voltammetry to compare their redox behavior to their [PhBP3] analogues. Complex 4 was also studied by SQUID magnetization and EPR spectroscopy to confirm its high-spin assignment, providing an interesting contrast to its previously described low-spin relative, [PhBP3]CoI. The difference in spin states observed for these two systems reflects the conformational rigidity of the [PhBp(3)(iPr)] ligand by comparison to [PhBP3], leaving the former less able to accommodate a JT-distorted electronic ground state

  DOI：

  10.1021/ic0343096

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。
• Considering Fe^II/IV Redox Processes as Mechanistically Relevant to the Catalytic Hydrogenation of Olefins by [PhBP<i>ⁱ</i>^Pr₃]Fe−H<i>_x</i> Species
  作者：Erin J. Daida、Jonas C. Peters

  DOI：10.1021/ic0488583

  日期：2004.11.1

  precursors, [PhBP(iPr)(3)]Fe-R ([PhBP(iPr)(3)] = [PhB(CH(2)P(i)Pr(2))(3)](-); R = Me (2), R = CH(2)Ph (3), R = CH(2)CMe(3) (4)) have been prepared from [PhBP(iPr)(3)]FeCl (1) that serve as precatalysts for the room-temperature hydrogenation of unsaturated hydrocarbons (e.g., ethylene, styrene, 2-pentyne) under atmospheric H(2) pressure. The solid-state crystal structures of 2 and 3 are presented. To gain

  几种配位不饱和拟四面体铁（II）前体[PhBP（iPr）（3）] Fe-R（[PhBP（iPr）（3）] = [PhB（CH（2）P（i）Pr（2））（ 3）]（-）； R = Me（2），R = CH（2）Ph（3），R = CH（2）CMe（3）（4））由[PhBP（iPr）（3 ）] FeCl（1）用作在大气压H（2）压力下室温氢化不饱和烃（例如乙烯，苯乙烯，2-戊炔）的预催化剂。呈现了2和3的固态晶体结构。为了深入了解这些氢化反应的性质，制备并研究了许多[PhBP（iPr）（3）]-负载的氢化铁。在捕集的膦配体存在下室温氢化2-4个烷基，得到三氢化铁（IV）物种[PhBP（iPr）（3）] Fe（H）（3）（PR（3））（PR（ 3）= PMe（3）（5）; PR（3）= PEt（3）（6）; PR（3）= PMePh（2）（7））。这些在光谱上定义明确的三氢化物在溶液中会经历不同
• Dinitrogen Chemistry from Trigonally Coordinated Iron and Cobalt Platforms
  作者：Theodore A. Betley、Jonas C. Peters

  DOI：10.1021/ja036687f

  日期：2003.9.1

  This report establishes that trigonally coordinated "[PhBPiPr3]M" platforms (M = Fe, Co) will support both pi-acidic (N2) and pi-basic (NR) ligands at a fourth binding site. The N2 complexes of iron that are described are the first thoroughly characterized examples to exhibit a 4-coordinate geometry. Methylation of monomeric Fe0(N2)-} and Co0(N2)-} species successfully derivatizes the beta-N atom

  该报告确定了三角协调的“[PhBPiPr3]M”平台（M = Fe，Co）将在第四个结合位点同时支持 pi 酸性（N2）和 pi 碱性（NR）配体。所描述的铁的 N2 络合物是第一个完全表征的例子，展示了 4 坐标几何。单体 Fe0(N2)-} 和 Co0(N2)-} 物质的甲基化成功衍生出配位 N2 配体的 β-N 原子并提供二氮杂产物 FeII(N2Me)} 和 CoII(N2Me)}，分别。单核 M0(N2)- 物种的单电子氧化产生双核和合成通用 MI(N2)MI 复合物。这些后一种物质为“[PhBPiPr3]MI”亚基的化学提供了干净的途径。例如，
• 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
• An η3-H2SiR2 Adduct of [{PhB(CH2PiPr2)3}FeIIH]
  作者：Christine M. Thomas、Jonas C. Peters

  DOI：10.1002/anie.200502527

  日期：2006.1.23