[Pd(o-C6H4CH=CNC(O)OCPh)(MeCN)2]ClO4 | 1214747-35-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [Pd(o-C6H4CH=CNC(O)OCPh)(MeCN)2]ClO4
• 英文别名: acetonitrile;palladium(2+);(4Z)-2-phenyl-4-(phenylmethylidene)-1,3-oxazol-5-one;perchlorate
• CAS: 1214747-35-9
• 化学式: C₂₀H₁₆N₃O₂Pd*ClO₄
• 分子量: 536.237
• InChiKey: JFLGXWMYMCWYJE-VDOWVRHSSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -0.87
• 重原子数：
  31
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  161
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  [Pd(μ-Br)(o-C6H4CH=CNC(O)OCPh)]2 、 silver perchlorate 、 乙腈 以 acetonitrile 为溶剂， 生成 [Pd(o-C6H4CH=CNC(O)OCPh)(MeCN)2]ClO4
  参考文献：
  名称：

  Ortho-Palladation of (Z)-2-Aryl-4-Arylidene-5(4H)-Oxazolones. Structure and Functionalization

  摘要：

  Ortho-palladated complexes of (Z)-2-aryl-4-arylidene-5(4H)-oxazolones have been prepared through oxidative addition. The reaction of (Z)-2-phenyl-4-(2-bromobenzylidene)-5(4H)-oxazolone (4) with Pd-2(dba)(3)center dot CHCl3 gives the six-membered cyclopalladated dinuclear complex [Pd(mu-Br)(o-C6H4CH=CNC(O)OCPh)](2) (7). The reaction of 7 with PPh3 gives dinuclear 9, which incorporates one phosphine per Pd atom through cleavage of the Pd-N bond, and preserves the bromide bridging system. However, reaction with PPh2Me gives mononuclear 8, which incorporates two phosphines as a results of the cleavage of the mu-Br system and N displacement. In contrast, the reaction of 7 with pyridine gives complex 12 due to Simple cleavage of the Br bridge, leaving the N-bonding intact. Therefore, three different reaction pathways have been characterized. The reactivity of the Pd-C bond in 7 has also been examined, and functionalized oxazolones can be obtained. The reaction of 7 With PhI(OAc)(2) in acetic acid gives the starting oxazolone C6H4-2-Br-CH=CNC(O)OCPh (4), through the presumed oxidation of the Pd center and C-Br bond formation by reductive coupling. In contrast, the reaction of the acetate dimer 14 with PhI(OAc)(2) in acetic acid gives C6H4-2-OAc-CH=CNC(O)OCPh (20) through C-O coupling. When treatment of 7 with PhI(OAc)(2) is performed in MeOH or EtOH, the oxazolones C6H4-2-OR-CH=CNC(O)OCPh (R = Me (18), Et (19)) are obtained. The reaction of 7 with CO in alcohols ROH gives cleanly the oxazolones C6H4-2-CO2R-CH=CNC(O)OCPh (R = Me (21), Pr-i (22)) through CO migratory insertion into the Pd-C bond and further nucleophilic attack of the RO- fragment.

  DOI：

  10.1021/om901068f