Pd(phenyl)(acetato)(PPh₃)₂ | 171484-64-3

• 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(phenyl)(acetato)(PPh₃)₂
• 英文别名: PdPh(OAc)(PPh₃)₂；[PhPd(PPh3)2(CH3COO)]；[PdPh(O2CMe)(PPh3)2]；PhPd(PPh3)2(OAc)
• CAS: 171484-64-3；167227-37-4
• 化学式: C₄₄H₃₈O₂P₂Pd
• 分子量: 767.152
• InChiKey: DAEWZNFOLLHCAX-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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  四丁基溴化铵 、 Pd(phenyl)(acetato)(PPh₃)₂ 以 四氢呋喃 为溶剂， 生成 trans-bromo(phenyl)bis(triphenylphosphine)palladium(II)
  参考文献：
  名称：

  Pd（0）催化的磷-碳键形成。钯源和阴离子添加剂作用机理的综合研究

  摘要：

  Pd（PPh 3）4，Pd（dba）2，Pd（OAc）2和PdCl 2已被评估为通过芳基的交叉偶联形成钯催化的PC键的Pd（0）源卤化物与H-膦酸酯二酯。已经发现，最有效的催化体系可以由Pd（OAc）2生成，其中具有协调性乙酸根离子的Pd（II）和Pd（0）物种起着关键作用。确定了不同连接的Pd（II）配合物的反应性，并进行了31 P NMR光谱研究，为观察到的催化体系之间的差异提供了机械解释。

  DOI：

  10.1021/om700797k
• 作为产物：
  描述：

  di-μ-acetatodiphenylbis(triphenylphosphine)dipalladium(II) 在 2-methylthiophene 作用下， 以 1,4-二氧六环 为溶剂， 生成 Pd(phenyl)(acetato)(PPh₃)₂
  参考文献：
  名称：

  2-甲基噻吩的直接芳基化与隔离[PDAR（μ-O 2 CR）（PPH 3）] Ñ配合物：动力学及机理

  摘要：

  已经提出芳族化合物与芳基卤化物的钯催化的直接芳基化涉及芳基钯羧酸盐中间体。但是，几乎没有文献报道过分离的芳基钯配合物，可在不借助其他活化剂或促进剂的情况下对芳香族底物进行C–H键裂解。本文报道的是[PDAR（μ-O 2 CR）（PPH 3）] ñ复合物（1：Ar为PH，2-MEC 6 ħ 4，2,6-ME 2 ç 6 ħ 3 ; R = Me中，吨Bu）在没有添加剂的情况下与2-甲基噻吩（2）成功反应，得到5-芳基-2-甲基噻吩（3）高产。反应性随Ar基团的增加而增加，而庞大的新戊酸酯配体（R = t Bu）与乙酸酯配体（R = Me）相比降低了反应性。复杂1处于平衡与单体物种[PDAR（O 2 CR-κ 2 ö）（PPH 3）]（5）在溶液中，如通过IR光谱法确认。动力学研究表明，直接芳基化是通过5进行的，它经历了2的C–H键断裂。配合物1可以作为2与芳基溴化物直接芳基化的良好催化剂。

  DOI：

  10.1021/om300367k

文献信息

• Factors Controlling the Reactivity of Heteroarenes in Direct Arylation with Arylpalladium Acetate Complexes
  作者：Masayuki Wakioka、Yuki Nakamura、Yoshihiro Hihara、Fumiyuki Ozawa、Shigeyoshi Sakaki

  DOI：10.1021/om400636r

  日期：2013.8.12

  The palladium-catalyzed direct arylation of heteroarenes with aryl halides has emerged as a viable alternative to conventional cross-coupling reactions. This paper reports a detailed mechanistic study on factors controlling the reactivity of heteroarenes in direct arylation with well-defined models of the presumed intermediate [PdAr(O2CMe-κ2O)L] (1). Although recent theoretical studies have provided

  钯催化的杂芳烃与芳基卤化物的直接芳基化已成为常规交叉偶联反应的可行替代方法。本文报道上控制杂芳烃的直接芳基化与推测中间体[PDAR（O的定义良好的模型的反应性因素的详细机理研究2 CME-κ 2 ö）L]（1）。尽管最近的理论研究对C–H键断裂机理进行了1的合理描述，但迄今为止测试的其模型化合物的反应性显然低于预期。我们发现，[PDPH（O 2 CME-κ 2 ö）（PPH 3）]（1A）和[钯（2,6--ME 2 ç 6 ħ 3）（O 2 CME-κ 2 ö）（PPH 3）]（1C），在原位产生分离自[PDPH（μ-O 2 CME）（PPH 3）] 2（图4a）和[钯（2,6--ME 2 ç 6 ħ 3）（μ-O 2 CME）（PPH 3）] 4（4C），分别以几乎定量的与各种杂芳烃的反应产量。杂芳烃的反应顺序通过竞争反应进行了评估，结果表明苯并噻唑（8尽管8的酸度（p K a = 27）远高于6的酸度（p
• Decelerating Effect of Alkenes in the Oxidative Addition of Phenyl Iodide to Palladium(0) Complexes in Heck Reactions
  作者：Christian Amatore、Emmanuelle Carré,、Anny Jutand、Youcef Medjour

  DOI：10.1021/om020439v

  日期：2002.10.1

  In DMF, the oxidative addition of PhI to Pd-0(PPh3)(4) or to the anionic Pd-0(PPh3)(3)(OAc)(-) is slower in the presence of an alkene (styrene, methyl acrylate). Indeed, the concentration of the reactive Pd-0(PPh3)(2) or PdO(PPh3)(2)(OAc)(-) complex decreases because of its coordination to the alkene to form the unreactive (eta(2)-CH2=CHR)Pd-0(PPh3)(2) (R = Ph, CO2Me) or (eta(2)-CH2= CHPh)Pd-0(PPh3)(2)(OAc)(-), respectively. As already evidenced in palladium-catalyzed Stille reactions, this work establishes that, in palladium-catalyzed Heck reactions as well, the nucleophile plays a role in the kinetics of the oxidative addition (decelerating effect), as soon as it may coordinate PdO complexes. This is an essential observation, in view of the general belief that the nucleophile enters the catalytic cycle only at the stage of the attack on the aryl-Pd-II complex formed in the oxidative addition. Whenever the oxidative addition is not rate determining, the decelerating effect of the alkene on this reaction is in favor of a higher efficiency of the catalytic cycle.
• The First Isolable Organopalladium Formato Complexes: Synthesis, Characterization, and X-ray Structure. Facile and Convenient Thermal Generation of Coordinatively Unsaturated Palladium(0) Species
  作者：Vladimir V. Grushin、Corinne Bensimon、Howard Alper

  DOI：10.1021/om00007a028

  日期：1995.7

  [L(2)Pd(2)(R)(2)(mu-OH)(2)] complexes (L = PPh(3), R = Ph, Me) react with formic acid in benzene to give the first stable organopalladium formates, [L(2)Pd(2)(R)2(mu-HCOO)(2)] (1, R = Ph; 2, R = Me). Addition of L to 1 and 2 results in the formation of the less stable, but still isolable, [L(2)Pd(R)(HCOO)] (3, R = Ph; 4, R = Me). Complexes 1-4 have been characterized by elemental analysis and NMR and IR spectral data. The structure of 2 has been,confirmed by X-ray analysis of its 1:1.5 benzene solvate: monoclinic, space group P2(1)/n; a = 9.785(4) Angstrom, b = 24.909(8) Angstrom, c = 18.854(7) Angstrom, beta = 102.92(3)degrees; V = 4479(3) Angstrom, Z = 4; D-calcd = 1.441 g/cm(3); R = 0.044, R(w) = 0.066. The thermal decomposition of 4-4 in benzene or toluene at 30-55 degrees C gives CO2, RH, and highly reactive [L(n)Pd] (n = 1, 2). An exchange between the sigma-Me groups and phenyls of the PPh(3) ligand is observed in the course of the thermal decomposition of 2 in toluene at 55 degrees C. The thermolysis of 1 in the presence of PhI gives rise to [L(2)Pd(2)(Ph)(2)(mu-I)(2)] (5); likewise, the decomposition of 2 in the presence of Mel furnishes [L(2)Pd(2)(Me)(2)(mu-I)(2)] (6). However, when 1 is decomposed in the presence of Mel, both 5 and 6 are formed, with the ratio of 5 to 6 being higher at higher concentrations of MeI. A similar effect is observed when 2 is thermolyzed in the presence of PhI. This ''reverse'' selectivity leads to the recognition of two distinct mechanisms governing the Pd-catalyzed reductive dehalogenation of aryl halides with formate anion.
• Evidence for the Ligation of Palladium(0) Complexes by Acetate Ions: Consequences on the Mechanism of Their Oxidative Addition with Phenyl Iodide and PhPd(OAc)(PPh3)2 as Intermediate in the Heck Reaction
  作者：Christian Amatore、Emmanuelle Carre、Anny Jutand、Mohamed Amine M'Barki、Gilbert Meyer

  DOI：10.1021/om00012a029

  日期：1995.12

  Addition of acetate anions to solutions of Pd-0(PPh(3))(4) results in the formation of anionic species in which the acetate ion coordinates the palladium(0) center, Pd-0(PPh(3))(3)(OAc)(-), which is in equilibrium with the less ligated complex, Pd-0(PPh(3))(2)(OAc)(-). The latter undergoes oxidative addition with phenyl iodide to afford a mixture of PhPdI(PPh(3))(2) and PhPd(OAc)-(PPh(3))(2). Acetate ions react with PhPdI(PPh(3))(2) to afford PhPd(OAc)(PPh(3))(2). Mixtures ofPd(OAc)(2) and nPPh(3) (n greater than or equal to 4), commonly used as catalysts in Heck reactions, afford a palladium(0) complex that is ligated by one acetate ion, yielding the anionic species Pd-0(PPh(3))(3)(OAc)(-) and Pd-0(PPh(3))(2)(OAc)(-). The latter reacts with phenyl iodide. However, this reaction does not afford the expected PhPdI(PPh3)2 complex but instead affords PhPd(OAc)(PPh(3))(2). Reaction of PhPd(OAc)(PPh(3))(2) with styrene results in the formation of stilbene, demonstrating that PhPd(OAc)(PPh(3))2 is an intermediate in the Heck reaction.