{Pd(2(diphenylphosphino)pyridine)Cl2} | 135973-16-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: {Pd(2(diphenylphosphino)pyridine)Cl2}
• 英文别名: [PdCl2(2-(diphenylphosphino)pyridine-P,N)]；[PdCl2(PPh2py-P,N)]；[Pd(κ2-2-pyridyldiphenylphosphine)Cl2]；Dichloropalladium;diphenyl(pyridin-2-yl)phosphane
• CAS: 135973-16-9
• 化学式: C₁₇H₁₄Cl₂NPPd
• 分子量: 440.605
• InChiKey: LRZFNNQZGQQEGO-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.22
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-丁基咪唑 、 ammonium hexafluorophosphate 、 {Pd(2(diphenylphosphino)pyridine)Cl2} 以 二氯甲烷 为溶剂， 反应 16.0h， 以90%的产率得到[PdCl(2-(diphenylphosphino)pyridine-P,N)(N-butylimidazole)](PF6)
  参考文献：
  名称：

  膦胺-Pd（II）-咪唑配合物的开发：对室温Suzuki-Miyaura交叉偶联反应的影响

  摘要：

  的反应Ñ甲基咪唑（N-MEIM）和Ñ -butylimidazole与复合物（N-BuIm）的PdCl 2（PPH 2 PY-P，N）]和[的PdCl 2（PPH 2 Etpy-P，N）]在NH 2 PF 6存在下于室温下在N 2下提供四种新的阳离子Pd（II）络合物[PdCl（PPh 2 py–P，N）（N-MeIm）]（PF 6）（1），[PdCl （PPh 2 py–P，N）（N-BuIm）] [PF 6）（2），[PdCl（PPh 2 Etpy–P，N）（N‐MeIm）]（PF 6）（4）和[PdCl （PPh 2Etpy-P，N）（N-BuIm）]（PF 6）（5）具有良好的收率，其中PPh 2 py是2-（二苯基膦基）吡啶，PPh 2 Etpy是2- {2-（二苯基膦基）乙基}吡啶）。配合物已得到充分表征。在室温下研究了这些络合物的催化活性对铃木-宫浦的交叉偶联反应。与其他类似

  DOI：

  10.1002/aoc.3029
• 作为产物：
  描述：

  二(氰基苯)二氯化钯 、 二苯基-2-吡啶膦 以 二氯甲烷 为溶剂， 生成 {Pd(2(diphenylphosphino)pyridine)Cl2}
  参考文献：
  名称：

  Arena, Carmela Grazia; Rotondo, Enrico; Faraone, Felice, Organometallics, 1991, vol. 10, # 11, p. 3877 - 3885

  摘要：

  DOI：

文献信息

• The synthesis of, and characterization of the dynamic processes occurring in Pd(ii) chelate complexes of 2-pyridyldiphenylphosphine
  作者：Jianke Liu、Chacko Jacob、Kelly J. Sheridan、Firas Al-Mosule、Brian T. Heaton、Jonathan A. Iggo、Mark Matthews、Jeremie Pelletier、Robin Whyman、Jamie F. Bickley、Alexander Steiner

  DOI：10.1039/b918162h

  日期：——

  Pd(II) complexes in which 2-pyridyldiphenylphosphine (Ph2Ppy) chelates the Pd(II) centre have been prepared and characterized by multinuclear NMR spectroscopy and by X-ray crystallographic analysis. trans-[Pd(κ1-Ph2Ppy)2Cl2] is transformed into [Pd(κ2-Ph2Ppy)(κ1-Ph2Ppy)Cl]Cl by the addition of a few drops of methanol to dichloromethane solutions, and into [Pd(κ2-Ph2Ppy)(κ1-Ph2Ppy)Cl]X by addition of AgX or TlX, (X = BF4−, CF3SO3− or MeSO3−). [Pd(κ1-Ph2Ppy)2(p-benzoquinone)] can be transformed into [Pd(κ2-Ph2Ppy)(κ1-Ph2Ppy)(MeSO3)][MeSO3] by the addition of two equivalents of MeSO3H. Addition of further MeSO3H affords [Pd(κ2-Ph2Ppy)(κ1-Ph2PpyH)(MeSO3)][MeSO3]2. Addition of two equivalents of CF3SO3H, MeSO3H or CF3CO2H and two equivalents of Ph2Ppy to [Pd(OAc)2] in CH2Cl2 or CH2Cl2–MeOH affords [Pd(κ2-Ph2Ppy)(κ1-Ph2Ppy)X]X, (X = CF3SO3−, MeSO3− or CF3CO2−), however addition of two equivalents of HBF4·Et2O affords a different complex, tentatively formulated as [Pd(κ2-Ph2Ppy)2]X2. Addition of excess acid results in the clean formation of [Pd(κ2-Ph2Ppy)(κ1-Ph2PpyH)(X)]X2. In methanol, addition of MeSO3H and three equivalents of Ph2Ppy to [Pd(OAc)2] affords [Pd(κ2-Ph2Ppy)(κ1-Ph2Ppy)2][MeSO3]2 as the principal Pd-phosphine complex. The fluxional processes occuring in these complexes and in [Pd (κ1-Ph2Ppy)3Cl]X, (X = Cl, OTf) and the potential for hemilability of the Ph2Ppy ligand has been investigated by variable-temperature NMR. The activation entropy and enthalpy for the regiospecific fluxional processes occuring in [Pd(κ2-Ph2Ppy)(κ1-Ph2Ppy)2][MeSO3]2 have been determined and are in the range −10 to −30 J mol−1 K−1 and ca. 30 kJ mol−1 respectively, consistent with associative pathways being followed. The observed regioselectivities of the exchanges are attributed to the constraints imposed by microscopic reversibility and the small bite angle of the Ph2Ppy ligand. X-Ray crystal structure determinations of trans-[Pd(κ1-Ph2Ppy)2Cl2], [Pd(κ2-Ph2Ppy)(κ1-Ph2Ppy)Cl][BF4], [Pd(κ1-Ph2Ppy)2(p-benzoquinone)], trans-[Pd(κ1-Ph2PpyH)2Cl2][MeSO3]2, and [Pd(κ1-Ph2Ppy)3Cl](Cl) are reported. In [Pd(κ2-Ph2Ppy)(κ1-Ph2Ppy)Cl][BF4] a donor–acceptor interaction is seen between the pyridyl-N of the monodentate Ph2Ppy ligand and the phosphorus of the chelating Ph2Ppy resulting in a trigonal bipyramidal geometry at this phosphorus.

  制备了 2-吡啶二苯基膦 (Ph2Ppy) 螯合 Pd(II) 中心的 Pd(II) 配合物，并通过多核 NMR 光谱和 X 射线晶体分析对其进行了表征。通过向二氯甲烷溶液中添加几滴甲醇，反式-[Pd(κ1-Ph2Ppy)2Cl2]转化为[Pd(κ2-Ph2Ppy)(κ1-Ph2Ppy)Cl]Cl，并转化为[Pd(κ2-Ph2Ppy) )(κ1-Ph2Ppy)Cl]X 通过添加 AgX 或 TlX，（X = BF4−、CF3SO3− 或 MeSO3−）。通过添加两当量的 MeSO3H，[Pd(κ1-Ph2Ppy)2(对苯醌)]可以转化为 [Pd(κ2-Ph2Ppy)(κ1-Ph2Ppy)(MeSO3)][MeSO3]。进一步添加 MeSO3H 得到 [Pd(κ2-Ph2Ppy)(κ1-Ph2PpyH)(MeSO3)][MeSO3]2。将两当量的 CF3SO3H、MeSO3H 或 CF3CO2H 和两当量的 Ph2Ppy 添加到 CH2Cl2 或 –MeOH 中的 [Pd(OAc)2] 中，得到 [Pd(κ2-Ph2Ppy)(κ1-Ph2Ppy)X]X，(X = CF3SO3 -、MeSO3- 或 CF3CO2-），但是添加两当量的 H ·Et2O 会得到不同的复合物，暂定为 [Pd(κ2-Ph2Ppy)2]X2。添加过量的酸导致 [Pd(κ2-Ph2Ppy)(κ1-Ph2PpyH)(X)]X2 的干净形成。在甲醇中，将 MeSO3H 和三当量的 Ph2Ppy 添加到 [Pd(OAc)2] 中，得到 [Pd(κ2-Ph2Ppy)(κ1-Ph2Ppy)2][MeSO3]2 作为主要的 Pd-膦络合物。这些配合物和 [Pd (κ1-Ph2Ppy)3Cl]X (X = Cl, OTf) 中发生的通量过程以及 Ph2Ppy 配体的半稳定性的潜力已通过变温 NMR 进行了研究。 [Pd(κ2-Ph2Ppy)(κ1-Ph2Ppy)2][MeSO3]2 中发生的区域特异性通量过程的活化熵和焓已确定，范围为 -10 至 -30 J mol−1 K−1和约。分别为 30 kJ mol−1，与所遵循的关联路径一致。观察到的交换区域选择性归因于微观可逆性和 Ph2Ppy 配体的小咬角所施加的限制。反式-[Pd(κ1-Ph2Ppy)2Cl2]、[Pd(κ2-Ph2Ppy)(κ1-Ph2Ppy)Cl][ ]、[Pd(κ1-Ph2Ppy)2(对苯醌)的X射线晶体结构测定]、反式-[Pd(κ1-Ph2PpyH)2Cl2][MeSO3]2 和 [Pd(κ1-Ph2Ppy)3Cl](Cl) 已报道。在 [Pd(κ2-Ph2Ppy)(κ1-Ph2Ppy)Cl][ ] 中，单齿 Ph2Ppy 配体的吡啶基-N 和螯合 Ph2Ppy 的磷之间存在供体-受体相互作用，从而形成三角双锥几何形状。磷。
• An effective strategy for immobilizing a homogeneous palladium complex onto silica: Efficient and reusable catalyst for Suzuki–Miyaura reactions
  作者：Chandan Sarmah、Debojeet Sahu、Pankaj Das

  DOI：10.1016/j.catcom.2013.06.039

  日期：2013.11

  A simple strategy has been adopted to immobilize a homogeneous palladium complex onto silica gel by introducing 4-pyridinecarbaldehyde into the coordination sphere of palladium. The material has been characterized by FTIR, BET measurements, XRD, SEM-EDX, and ICP-AES. The supported material has acted as an efficient catalyst for the Suzuki-Miyaura reactions of aryl halides with low palladium loading (0.04 mol%) in environment-friendly reaction media. In addition, the heterogeneous catalyst could retain the high activity of the homogeneous counterpart catalyst, showed almost no leaching, and could be reused several times without loss of activity. (C) 2013 Elsevier B.V. All rights reserved.