[Pd{κ²(C,C)-C₆H₄PPh₂C(H)CO(C₆H₄-NO₂-4)}(μ-Cl)]₂ | 1286835-50-4

• 英文名称: [Pd{κ²(C,C)-C₆H₄PPh₂C(H)CO(C₆H₄-NO₂-4)}(μ-Cl)]₂
• 英文别名: [Pd2(μ-Cl)2(κ2(C,C)-C6H4PPh2CHC(O)C6H4NO2)2]
• CAS: 1286835-50-4；1287312-88-2；1287312-87-1；1287312-89-3
• 化学式: C₅₂H₃₈Cl₂N₂O₆P₂Pd₂
• 分子量: 1132.58
• InChiKey: NCPYFAIQSVRPQN-UHFFFAOYSA-L

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：

  [Pd{κ²(C,C)-C₆H₄PPh₂C(H)CO(C₆H₄-NO₂-4)}(μ-Cl)]₂ 、 sodium azide 以 甲醇 为溶剂， 反应 12.0h， 以70%的产率得到[Pd{κ2(C,C)-C₆H₄PPh₂C(H)CO(C₆H₄-NO_2-4)}(μ-N₃)]₂
  参考文献：
  名称：

  Synthesis, spectral characterization, crystal structure and in vitro DNA/protein binding studies of phosphorous ylide palladacyclic complexes containing azide group

  摘要：

  The reaction between (4-nitrobenzoylmethylene)triphenylphosphorane Pd(II) complex [Pd{kappa(2)(C,C)-C-6 H4PPh2C(H)CO(C6H4 NO2-41)}(mu-Cl)](2) and excess of NaN3 resulted in the mu-N3 bridged Pd(II) complex [Pd{kappa(2)(C,C)-C(6)H(4)Pph(2)C(H)CO(C6H4 NO2-4)}(mu-N-3)](2) (1), which underwent bridge cleavage reactions with monodentate ligands to afford the monomeric, neutral complexes [Pd{kappa(2)(C,C)-C6H4PPh2C(H)CO(C-6 H-4 NO2-4)}N-3(L)] (L = Me3Py (1a), PPh3 (1b)). The complexes were identified and characterized by elemental analyses, infrared (IR), H-1, C-13{H-1} and P-31{H-1} NMR spectroscopy. The molecular structure of 1b was determined by single-crystal X-ray diffraction. The interactions of complexes with FS-DNA were investigated using UV absorption and fluorescence spectra. The results suggested that both complexes could interact with FS-DNA through the intercalation mode and follow the binding affinity order of 1a > 1b. The reactivity toward protein BSA revealed that the quenching of BSA fluorescence by the two complexes are static quenching, and complex la exhibits a higher BSA-binding ability than the complex 1b. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jphotobiol.2015.01.012
• 作为产物：
  描述：

  palladium diacetate 、 1-(4-nitro-phenyl)-2-(triphenyl-λ⁵-phosphanylidene)-ethanone 、 sodium chloride 以 二氯甲烷 为溶剂， 以77%的产率得到[Pd{κ²(C,C)-C₆H₄PPh₂C(H)CO(C₆H₄-NO₂-4)}(μ-Cl)]₂
  参考文献：
  名称：

  Orthopalladation of phosphorus ylides in endo position with bidentate ligands

  摘要：

  The ortho-metallated complexes [Pd(2){kappa(2)(C,C)-C(6)H(4)(PPh(2)CHC(O)C(6)H(5)R}(2)(mu-Cl)(2)] (R = Ph (1a), NO(2) (1b), Br (1c)) were prepared by refluxing equimolar mixtures of Ph(3)P=CHC(O)C(6)H(5)R, (R = Ph, NO(2), Br) and Pd(OAc)(2) in MeOH, followed by an excess of NaCl. The dinuclear complexes (1a-1c) react with silver trifluoromethylsulfonate and bidentate ligands [L = bipy (2,2'-bipyridine), phen (phenanthroline), dppe (bis(diphenylphosphino)ethane), dppp (bis(diphenylphosphino)propane)] giving the mononuclear stabilized orthopalladated complexes in endo position [Pd{kappa(2)(C,C)-C(6)H(4)(PPh(2)CHC(O)R}L](OTf) [R = Ph, L = phen (2a), bipy (3a), dppe (4a), dppp (5a); R = NO2, L = phen (2b), bipy (3b), dppe (4b), dppp (5b); R = Br, L = phen (2c), bipy (3c), dppe (4c), dppp (5c); OTf = trifluoromethylsulfonate anion]. Orthometalation and ylidic C-coordination are demonstrated by an X-ray diffraction study of 2c and 3c. In the structures, the palladium atom shows a slightly distorted square-planar coordination geometry. Published by Elsevier Ltd.

  DOI：

  10.1016/j.poly.2010.12.014
• 作为试剂：
  描述：

  4-氯苯甲醛 、 苯硼酸 在 potassium phosphate monohydrate 、 [Pd{κ²(C,C)-C₆H₄PPh₂C(H)CO(C₆H₄-NO₂-4)}(μ-Cl)]₂ 作用下， 以 氘代甲醇-d 为溶剂， 反应 4.0h， 以76.5%的产率得到对苯基苯甲醛
  参考文献：
  名称：

  Catalytic activity of some palladium complexes of a phosphorus ylide and the structure of a 2-phenylaniline-based palladacycle complex

  摘要：

  A six-membered N,C-palladacycle bearing the 2-phenylaniline bidentate ligand (1) and three other palladium complexes of a phosphorus ylide (2, 3 and 4) were utilized in Suzuki reactions between phenylboronic acid and a number of aryl bromides and chlorides. The complexes were found to be capable homogeneous catalysts for a variety of substrates, affording the coupled products in good to excellent yields. The structure of compound I, determined by X-ray diffraction, is also reported. (c) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2013.04.055

文献信息

• Synthesis, structural and theoretical studies of Pd(II) complexes containing an orthometallated C,C-chelating phosphorus ylide
  作者：Kazem Karami、Mina Salimian、Mahboubeh Hosseini-Kharat、Giuseppe Bruno、Hadi Amiri Rudbari、Hossein Tavakol

  DOI：10.1016/j.poly.2013.05.051

  日期：2013.9

  The phosphorus ylide [Ph3PCHC(O)C6H4-NO2-4] (1) reacted with Pd(OAc)(2) to give the C,C-orthometallated complexes [Pdkappa(2)(C,C)-C6H4PPh2C(H)CO(C6H4-NO2-4)}(mu-X)](2) (X = Cl (2); X = Br (3)) as a mixture of isomers, which underwent bridge cleavage reactions with monodentate ligands to afford the monomeric, neutral Pd(II) complexes [Pdkappa(2)(C,C)-C6H4PPh2C(H)CO(C6H4-NO2-4)}X(L)] (X = Cl, L = Me3Py (4), PPh3 (5); X = Br, L = Me3Py (6), 4-MePy (7), PPh3 (8). The complexes were identified and characterized by spectroscopic studies (IR and NMR). The X-ray single crystal analysis of 6 and 7 revealed the presence of an orthometallated C6H4-2-PPh2 unit and a C-linked ylide, Pd-C(H). In the crystal structure of 6, the location of the Me3Py ligand is trans to the Pd-C-ylide, according to the anti-symbiotic effect, whereas in 7 the 4-MePy ligand is preferentially cis to the Pd-C-ylide. Density functional theory (DFT) calculations in the reaction solvent (dichloromethane) indicated that the trans isomers of 6 and 7 are 3.03 and 0.70 kcal/mol more stable than their cis isomers, respectively. (C) 2013 Elsevier Ltd. All rights reserved.