| 164019-44-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• CAS: 164019-44-7
• 化学式: C₅₀H₇₆O₃P₂Pd
• 分子量: 893.519
• InChiKey: HGXDBXVNFADZHK-UHFFFAOYSA-M

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：

  生成 Pd(O2CPh)2(P(Cy)3)2
  参考文献：
  名称：

  Indirect Formation of Carboxylic Acids via Anhydrides in the Palladium-Catalyzed Hydroxycarbonylation of Aromatic Halides

  摘要：

  The carbonylation of [(Ph(3)P)(2)Pd(2)Ph(2)(mu-OH)(2)] (2) in the presence of PhI results in the quantitative formation of benzoic anhydride and [(Ph(3)P)(2)Pd-2(PhCO)(2)(mu-I)(2)] (3). This transformation contributes to some extent to the production of benzoic acid from haloarenes, CO, and alkali, catalyzed by [(Ph(3)P)(2)PdCl2], the latter being converted to 2 under the reaction conditions. Phenyl- and benzoylpalladium benzoates are likely key intermediates in the indirect formation of the acid, via the anhydride, by the carbonylation of 2. One such complex, [L(2)Pd(Ph)(PhCOO)] (5, L Cy(3)P), was isolated from the carbonylation of [(Cy(3)P)(2)Pd(2)Ph(2)(mu-OH)(2)] (4) in hexane. The related complexes, [L(2)Pd(2)Ph(2)(mu-PhCOO)(2)] (6, L = PPh(3); 7, L = PCy(3)), were prepared from benzoic acid and hydroxo complexes 2 and 4, respectively. Treatment of 6 and 7 with the corresponding phosphine afforded [L(2)pd(ph)(phCOO)] (8, L = PPh(3); 5, L = PCy(3)). When 6-8 were reacted with CO in benzene, benzoic anhydride was readily formed, whereas in the case of 5 both carbonylation and reductive elimination were sluggish. Crystallographic data for 6 (1:2 chloroform solvate): space group Peen, a = 22.499(4) Angstrom, b = 10.992(3) Angstrom, c = 24.514(6) Angstrom, V = 6062.4(23) Angstrom(3), Z = 4, R = 0.056, and R(w) = 0.038.

  DOI：

  10.1021/ja00120a012
• 作为产物：
  描述：

  生成
  参考文献：
  名称：

  Indirect Formation of Carboxylic Acids via Anhydrides in the Palladium-Catalyzed Hydroxycarbonylation of Aromatic Halides

  摘要：

  The carbonylation of [(Ph(3)P)(2)Pd(2)Ph(2)(mu-OH)(2)] (2) in the presence of PhI results in the quantitative formation of benzoic anhydride and [(Ph(3)P)(2)Pd-2(PhCO)(2)(mu-I)(2)] (3). This transformation contributes to some extent to the production of benzoic acid from haloarenes, CO, and alkali, catalyzed by [(Ph(3)P)(2)PdCl2], the latter being converted to 2 under the reaction conditions. Phenyl- and benzoylpalladium benzoates are likely key intermediates in the indirect formation of the acid, via the anhydride, by the carbonylation of 2. One such complex, [L(2)Pd(Ph)(PhCOO)] (5, L Cy(3)P), was isolated from the carbonylation of [(Cy(3)P)(2)Pd(2)Ph(2)(mu-OH)(2)] (4) in hexane. The related complexes, [L(2)Pd(2)Ph(2)(mu-PhCOO)(2)] (6, L = PPh(3); 7, L = PCy(3)), were prepared from benzoic acid and hydroxo complexes 2 and 4, respectively. Treatment of 6 and 7 with the corresponding phosphine afforded [L(2)pd(ph)(phCOO)] (8, L = PPh(3); 5, L = PCy(3)). When 6-8 were reacted with CO in benzene, benzoic anhydride was readily formed, whereas in the case of 5 both carbonylation and reductive elimination were sluggish. Crystallographic data for 6 (1:2 chloroform solvate): space group Peen, a = 22.499(4) Angstrom, b = 10.992(3) Angstrom, c = 24.514(6) Angstrom, V = 6062.4(23) Angstrom(3), Z = 4, R = 0.056, and R(w) = 0.038.

  DOI：

  10.1021/ja00120a012

文献信息

• Formation, Characterization, and Reactivity of Acyl Palladium Complexes in Pd(OAc)₂/PCy₃-Catalyzed Transformation of Acyl Fluorides
  作者：Hiroyuki Hattori、Yohei Ogiwara、Norio Sakai

  DOI：10.1021/acs.organomet.2c00165

  日期：2022.6.27

  ium complexes via a stoichiometric reaction between benzoyl fluorides, Pd(OAc)2, a hydrosilane and a phosphine is reported. NMR studies of the acyl palladium complex reveal the generation mechanism of the complex and indicate that the complex is a reaction intermediate in a palladium-catalyzed reduction of acyl fluorides using a hydrosilane. Furthermore, the acyl(carboxylato)palladium complex provides

  报道了通过苯甲酰氟、Pd(OAc) 2、氢硅烷和膦之间的化学计量反应形成苯甲酰基(苯甲酸根)钯配合物。酰基钯配合物的 NMR 研究揭示了配合物的生成机理，并表明该配合物是使用氢硅烷的钯催化的酰基氟还原反应的中间体。此外，酰基(羧基)钯络合物通过与另一种酰基氟的化学计量反应提供衍生自酰基络合物的酰基氟。