[Pd(C,N-C6H3(MeO-4)(C(O)N=PPh3-2))(bipy)]ClO4 | 944735-00-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: [Pd(C,N-C6H3(MeO-4)(C(O)N=PPh3-2))(bipy)]ClO4
• CAS: 944735-00-6
• 化学式: C₃₆H₂₉N₃O₂PPd*ClO₄
• 分子量: 772.49
• InChiKey: GBMNBBMZGIJFIV-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  2,2'-联吡啶 、 exo-[Pd(μ-Cl)(C,N-C6H3(4-OMe)(C(O)N=PPh3-2))]2 、 silver perchlorate 以 not given 为溶剂， 生成 [Pd(C,N-C6H3(MeO-4)(C(O)N=PPh3-2))(bipy)]ClO4
  参考文献：
  名称：

  Divergent Behavior in the Cyclopalladation of Phosphorus Ylides and Iminophosphoranes

  摘要：

  The cyclopalladation of the stabilized iminophosphoranes Ph3PNC(O)C6H4R (R = H 1a, 4-OMe 1b, 3-OMe 1c, 2-Me 1d, 3-Me 1e) results in the regioselective activation of the ortho CH bond of the benzamide ring, giving exo-[Pd(mu-Cl){C,N-C6H3(R){C(O)NPPh3-2}}](2) (R = H 2a, 5-OMe 2b, 4-OMe 2c, 3-Me 2d, 4-Me 2e). The palladated ligand behaves as a strong C,N-chelating group and cannot be easily displaced by other chelating ligands. This is clear from the reaction of 2c with Tl(acac), py, or AgClO4/LandL, which gives [Pd(acac){C,N-C6H3(MeO-4){C(O)NPPh3-2}}] (3c), [PdCl{C,N-C6H3(MeO-4){C(O)NPPh3-2}}(py)] (4c), or [Pd{C,N-C6H3(MeO-4){C(O)NPPh3-2}}(LandL)]ClO4 (LandL = dppe 5c, bipy 6c, phen 7c). However, Pd(OAc)(2) reacts with the ylides Ph3PCHC(O)C6H4R (R = H 8a, 3-OMe 8b, 2,5-(OMe)(2) 8c) to give the C,C-orthometalated complexes [Pd(mu-Cl){C,C-[C6H4(PPh2CHC(O)C6H4R)-2]}] (R = H 9a, 3-OMe 9b, 2,5-(OMe)(2) 9c), which are also regioselectively obtained. The C,C-metalated chelate is very stable, as shown by the reactions of 9b with Tl(acac), PPh3, and AgClO4/LandL. The X-ray structures of 2d and 9b have been determined. Unexpectedly, the reaction of Pd(OAc)(2) with the ylide [Ph3PCHC(O)C6H3-2,4-(OMe)(2)] (16) gives the polymer [(mu-Cl)Pd{C6H4(PPh2CH-C(O)C6H2-3,5-(OMe)(2))-2}-kappa-C,C,C,O)Pd(mu-Cl)](n) (17) as a result of a double palladation, giving two types of metalacycles: in one of them, the Pd atom is bonded to the ylidic C alpha atom and has activated an ortho C(Ph)-H bond of the PPh3 group; in the other one, the Pd atom is bonded to the carbonyl oxygen and has activated an ortho C-H bond of the C6H3(OMe)(2) unit. This tetradentate ylide ligand is remarkably stable.

  DOI：

  10.1021/om7002877