(1,1’-bis(diphenylphosphino)ferrocene)Ni(CO)2 | 160260-01-5

• 英文名称: (1,1’-bis(diphenylphosphino)ferrocene)Ni(CO)2
• 英文别名: dicarbonyl[bis(diphenylphosphino)ferrocene]nickel(0)；[Ni(CO)₂(1,1′-bis(diphenylphosphino)ferrocene)]；(1,1’-bis(diphenylphosphino)ferrocene)Ni(CO)₂；(dppf)Ni(CO)₂；[Ni(CO)₂dppf]；((η5-C5H4PPh2)2Fe)Ni(CO)2；(fc(PPh2)2)Ni(CO)2
• CAS: 160260-01-5
• 化学式: C₃₆H₂₈FeNiO₂P₂
• 分子量: 669.102
• InChiKey: NSYTXJAPSZUUKW-UHFFFAOYSA-N

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

• 作为产物：
  描述：

  以 氘代甲苯 为溶剂， 反应 0.17h， 生成 (1,1’-bis(diphenylphosphino)ferrocene)Ni(CO)2
  参考文献：
  名称：

  配体对镍-酮配合物稳定性的电子效应

  摘要：

  合成了电子变体（dppf）Ni（乙烯酮）配合物，并对其进行了动力学分析，以对其通过羰基化/歧化成Ni-CO配合物和烯烃的分解过程进行动力学分析。含有给电子基团的配体稳定了这种配合物，而吸电子基团使它们不稳定。Hammett对分解反应的分析揭示了在速率确定步骤中负电荷的积累，这证实了过去的计算模型。

  DOI：

  10.1021/acs.organomet.8b00484

文献信息

• Comparison of dppf‐Supported Nickel Precatalysts for the Suzuki–Miyaura Reaction: The Observation and Activity of Nickel(I)
  作者：Louise M. Guard、Megan Mohadjer Beromi、Gary W. Brudvig、Nilay Hazari、David J. Vinyard

  DOI：10.1002/anie.201505699

  日期：2015.11.2

  Ni‐based precatalysts for the Suzuki–Miyaura reaction have potential chemical and economic advantages compared to commonly used Pd systems. Here, we compare Ni precatalysts for the Suzuki–Miyaura reaction supported by the dppf ligand in 3 oxidation states, 0, I and II. Surprisingly, at 80 °C they give similar catalytic activity, with all systems generating significant amounts of NiI during the reaction

  与常用的Pd系统相比，Suzuki-Miyaura反应的镍基预催化剂具有潜在的化学和经济优势。在这里，我们比较了dppf配体在3种氧化态（0，I和II）下对Suzuki-Miyaura反应的Ni预催化剂。出人意料的是，在80℃下它们得到类似的催化活性，其中所有系统产生显著的Ni的余在反应过程中。在室温下，易于获得的台式稳定的Ni II预催化剂具有很高的活性，可以偶联重要的合成杂环底物。我们的工作最终确定了Ni I物种与通常仅涉及Ni 0和Ni II配合物的反应有关。
• Anodic Mechanism of 1,1′‐Bis(diphenylphosphino)ferrocenedicarbonylnickel Determined by Low‐Temperature Spectroelectrochemistry
  作者：Mark R. Ringenberg、Florian Döttinger

  DOI：10.1002/ejic.201900150

  日期：2019.5.26

  [Ni(CO)2(dppf)] [1] dppf = 1,1′‐bis(diphenylphosphino)ferrocene} was made by reductive carbonylation of [NiCl2(dppf)] with [Fe(CO)5], similar to our recent report in Organometallics, 2019, 38, 586–592. Complex [1] showed two oxidation waves in the cyclic voltammogram. UV/Vis‐NIR spectroelectrochemistry (SEC) and IR SEC at –30 °C as well as computational support by means of DFT was used to assign the

  [Ni（CO）2（dppf）] [ 1 ] dppf = 1,1'-双（二苯基膦基）二茂铁}是通过[NiCl 2（dppf）]与[Fe（CO）5 ]的还原羰基化反应制得的我们最近在报告中金属有机化合物，2019，38，586-592。络合物[ 1 ]在循环伏安图中显示了两个氧化波。在–30°C下的UV / Vis-NIR光谱电化学（SEC）和IR SEC以及通过DFT的计算支持被用来指定氧化后两个金属原子的氧化态。单阳离子[ 1 ] +表现出很强的近红外吸收带，被描述为IVCT [Ni I →FeII ]和逆IVCT（iIVCT）或基于时间依赖性DFT（TD-DFT）的空穴转移[Fe II →Ni I ]。[ 1 ] +的IR SEC光谱显示出多个带，它们与两个相似的构型相关，一个带的自旋在两个金属原子上均离域化，第二个带的自旋主要位于Ni上。第二次氧化为[ 1 ] 2+发生在Ni原子上
• Ferrocenyl phosphane nickel carbonyls: Synthesis, solid state structure, and their use as catalysts in the oligomerization of ethylene
  作者：Dieter Schaarschmidt、Janett Kühnert、Sascha Tripke、Helmut G. Alt、Christian Görl、Tobias Rüffer、Petra Ecorchard、Bernhard Walfort、Heinrich Lang

  DOI：10.1016/j.jorganchem.2010.03.012

  日期：2010.5

  The synthesis of diverse ferrocenyl phosphane nickel carbonyls of type (FcPPh(2))Ni(CO)(3) (3), (FcPPh(2))(2)Ni(CO)(2) (4), fc(PR2Ni(CO)(3))(2) (R = Ph (6a), R = p-tolyl (6b)), and (fc(PPh2)(2)) Ni(CO)(2) (7) (eta(5)-C5H5)(eta(5)-C5H4)Fe, fc = (eta(5)-C5H4)(2)Fe) starting from FcPPh(2) (1), fc(PR2)(2) (R = Ph (5a); R = p-tolyl (5b)), and Ni(CO)(4) (2) is described. The structures of 3, 4, 6b, and 7 in the solid state are reported, intermolecular interactions by pi-pi-contacts are discussed. The behavior of 3, 4, 6a, 6b, and 7 towards the oligomerization of ethylene is reported. All compounds, except 4, were found to be inactive in homogeneous ethylene oligomerization, while they exhibit moderate activities (up to 660 kg prod/mol Ni h) in heterogeneous ethylene oligomerization experiments. (C) 2010 Elsevier B.V. All rights reserved.
• Systematic Variation of Bidentate Ligands Used in Aryl Halide Amination. Unexpected Effects of Steric, Electronic, and Geometric Perturbations
  作者：Blake C. Hamann、John F. Hartwig

  DOI：10.1021/ja9721881

  日期：1998.4.1

  This paper presents effects of varying bidentate phosphine steric properties, electronic properties, and bite angle on product ratios in the amination of aryl bromides. Comparisons of the ratios of amine products to dehydrohalogenation products showed that catalysts containing electron rich, modestly hindered phosphines with small bite angles (similar to 90 degrees) gave the best selectivities. Surprisingly, the arene side product formed from reaction of alkylamines deuterated in the N-H position or deuterated in the position or to the nitrogen showed low levels of deuterium incorporation in many examples. Steric properties and ligand bite angle had the greatest impact on the selectivity for monoarylation versus diarylation of primary amines: ligands with small bite angles gave higher monoarylation-to-diarylation ratios, as did ligands with increased steric bulk. Electron poor or sterically hindered bidentate phosphines reduced the amount of product resulting from aryl exchange of electron rich palladium-bound arenes with those of aryl groups on the phosphine ligands.