rac-[(C5H5)Fe(C5H3(P(C6H5)2)CH2C3H3N2CH3)][BF4] | 954149-79-2

• 英文名称: rac-[(C5H5)Fe(C5H3(P(C6H5)2)CH2C3H3N2CH3)][BF4]
• CAS: 954149-79-2
• 化学式: BF₄*C₂₇H₂₆FeN₂P
• 分子量: 552.142
• InChiKey: XPHRDEPFLCUUIC-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

• 作为反应物：
  描述：

  双(乙腈)氯化钯(II) 、 rac-[(C5H5)Fe(C5H3(P(C6H5)2)CH2C3H3N2CH3)][BF4] 在 (CH₃)3CONa 作用下， 以 acetonitrile 为溶剂， 以75%的产率得到cyclopenta-1,3-diene;iron(2+);[2-[(3-methyl-2H-imidazol-1-ium-2-id-1-yl)methyl]cyclopenta-2,4-dien-1-yl]-diphenylphosphane;palladium(2+);dichloride
  参考文献：
  名称：

  平面手性二茂铁基膦-NHC配体的钯配合物：不对称Suzuki-Miyaura反应的新催化剂

  摘要：

  仅以中等至良好的产率制备了具有平面手性的带有手性膦-N-杂环卡宾配体的空气稳定的中性和阳离子钯配合物，并通过NMR和X射线衍射研究表征。结果表明，它们以低产率（0.1-0.5 mol％），高收率和中等对映选择性（最高42％ee）催化芳基溴化物与芳基硼酸的不对称偶联。

  DOI：

  10.1021/om100125k
• 作为产物：
  描述：

  rac-[(C5H5)Fe(C5H3(P(C6H5)2S)CH2C3H3N2CH3)][BF4] 在 Raney Ni 作用下， 以 acetonitrile 为溶剂， 以95%的产率得到rac-[(C5H5)Fe(C5H3(P(C6H5)2)CH2C3H3N2CH3)][BF4]
  参考文献：
  名称：

  平面手性二茂铁基膦-NHC配体的钯配合物：不对称Suzuki-Miyaura反应的新催化剂

  摘要：

  仅以中等至良好的产率制备了具有平面手性的带有手性膦-N-杂环卡宾配体的空气稳定的中性和阳离子钯配合物，并通过NMR和X射线衍射研究表征。结果表明，它们以低产率（0.1-0.5 mol％），高收率和中等对映选择性（最高42％ee）催化芳基溴化物与芳基硼酸的不对称偶联。

  DOI：

  10.1021/om100125k

文献信息

• Contribution of heterobifunctional ligands to transition metal-catalysed C--C coupling reactions
  作者：Agnes LABANDE、Eric DEYDIER、Eric MANOURY、Jean-Claude DARAN、Catherine AUDIN、Rinaldo POLI

  DOI：10.3906/kim-1507-73

  日期：——

  In this account the authors' latest results in C-C coupling catalysis are reviewed. First, an efficient catalytic system for the Kumada-Tamao-Corriu coupling reaction based on NHC-phosphine (NHC = N-heterocyclic carbene) nickel complexes is presented. Then the use of palladium complexes of chiral ferrocenyl NHC-phosphines in the asymmetric Suzuki-Miyaura coupling reaction is reported. High catalytic activities and moderate enantioselectivities (ee up to 46%) were obtained. Chiral ferrocenyl phosphine-ethers were also tested in the asymmetric Suzuki-Miyaura reaction yielding good activities and moderate enantioselectivities (ee up to 37%). Finally, the original synthesis of a ferrocenyl rhodium(III) complex and its successful use as catalyst for a C-C coupling reaction via C-H activation of 2-phenylpyridine is presented.

  在这篇报道中，作者回顾了他们在C-C偶联催化方面的最新成果。首先，介绍了一种基于NHC-膦（NHC = N-杂环卡宾）镍复合物的高效催化体系，用于Kumada-Tamao-Corriu偶联反应。然后，报告了手性二茂铁NHC-膦的钯复合物在不对称Suzuki-Miyaura偶联反应中的应用，获得了高催化活性和适中的对映选择性（对映体富集率高达46%）。手性二茂铁膦醚在不对称Suzuki-Miyaura反应中也进行了测试，表现出良好的催化活性和适中的对映选择性（对映体富集率高达37%）。最后，介绍了一种二茂铁铑(III)复合物的原创合成及其成功作为催化剂通过C-H活化2-苯基吡啶进行C-C偶联反应的应用。
• Palladium(<scp>ii</scp>) complexes with planar chiral ferrocenyl phosphane–(benz)imidazol-2-ylidene ligands
  作者：Pauline Loxq、Nathalie Debono、Süleyman Gülcemal、Jean-Claude Daran、Eric Manoury、Rinaldo Poli、Bekir Çetinkaya、Agnès Labande

  DOI：10.1039/c3nj00863k

  日期：——

  We describe here the first examples of planar chiral ferrocenyl phosphane–benzimidazol-2-ylidene ligands and their coordination chemistry with palladium(II). All ligand precursors, namely enantiopure ferrocenyl phosphane–(benz)imidazolium salts, and all enantiopure palladium complexes have been fully characterised by 1H, 31P and 13C NMR, mass spectrometry and X-ray diffraction methods for seven examples. The potential of these very bulky bidentate ligands in catalysis was evaluated and compared to their imidazol-2-ylidene analogues. The influence of sterics was shown to be non-negligible as the bulkiest ligand gave the lowest activities in the asymmetric Suzuki–Miyaura reaction.

  我们在此介绍了平面手性二茂铁磷烷苯并咪唑-2-亚基配体及其与钯（II）的配位化学反应。通过 1H、31P 和 13C NMR、质谱和 X 射线衍射方法，对所有配体前体（即对映纯二茂铁磷烷苯并咪唑盐）和所有对映纯钯配合物进行了全面表征，共七个实例。对这些非常笨重的双齿配体的催化潜力进行了评估，并与它们的咪唑-2-亚基类似物进行了比较。结果表明，在不对称铃木-米亚乌拉反应中，最粗大配体的活性最低，因此立体结构的影响不可忽视。
• New (1‐Phosphanylferrocen‐1′‐ and ‐2‐yl)methyl‐Linked Diaminocarbene Ligands: Synthesis and Rhodium(I) Complexes
  作者：Agnès Labande、Jean‐Claude Daran、Eric Manoury、Rinaldo Poli

  DOI：10.1002/ejic.200601193

  日期：2007.3

  AbstractTwo ferrocenylmethanols, [1′‐(diphenylthiophosphanyl)ferrocen‐1‐yl]methanol (3) and [2‐(diphenylthiophosphanyl)ferrocen‐1‐yl]methanol (6), have been converted in one step into the 1,1′‐ and 1,2‐ferrocenediyl‐linked thiophosphane/N‐R‐imidazolium salts 4a,b and 7a,b (a: R = Me; b: R = 2,4,6‐Me3C6H2 or Mes). This straightforward method allows the linkage of an imidazolium group to a ferrocene unit with a nonsubstituted methylene bridge. After desulfurisation of the phosphane group, the ligands reacted with an RhI precursor, in the presence of tBuOK, to give cationic complexes 9a,b and 10a,b. All compounds were characterised by elemental analysis, NMR spectroscopy and mass spectrometry. The molecular structures of compounds 4a, 7a and 9a were determined by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)