Pd(p-C6H4CMe3)(benzylamine)2Br * benzylamine | 180400-92-4

• 英文名称: Pd(p-C6H4CMe3)(benzylamine)2Br * benzylamine
• CAS: 180400-92-4
• 化学式: C₇H₉N*C₂₄H₃₁BrN₂Pd
• 分子量: 641.003
• InChiKey: ZXZFVRCZGYTXJL-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：
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• 环数：
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• sp3杂化的碳原子比例：
  None
• 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：

  Pd(p-C6H4CMe3)(benzylamine)2Br * benzylamine 、 苄胺-D2 以 氘代苯 为溶剂， 生成 Pd(p-C6H4CMe3)(α,α-benzylamine-d2)2Br * α,α-benzylamine-d2
  参考文献：
  名称：

  Kinetics and Mechanism of the Formation of Palladium Bis(benzylamine) Complexes from Reaction of Benzylamine with Palladium Tri-o-tolylphosphine Mono(amine) Complexes

  摘要：

  The kinetics of the conversion of the palladium mono(benzylamine) complex Pd[P(o-tol)(3)](p-C6H4CMe3)H-2-NBn]Br (2) to the bis(benzylamine) complex Pd(p-C6H4CMe3)[H2NBn](2)Br (3) established the second-order rate law: Rate = k(1)[2][H2NBn], where Delta H-double dagger = 13.8 +/- 0.3 kcal mol(-1) and Delta S-double dagger = -29.7 +/- 0.8 eu. Kinetics were consistent with a mechanism initiated by direct attack of benzylamine on 2 via an associative or interchange mechanism. Benzylamine exchange with both 2 and 3 was > 1.5 x 10(3) times faster than conversion of 2 to 3 under comparable conditions. Complex 2 underwent phosphine exchange in the presence of P(1-naphthyl)(3) to form Pd[P(1-naphthyl)(3)](P-C6H4CMe3)[H2NBn]Br (9). Kinetics of the conversion of 9 to 2 were consistent with associative solvolysis of 9 to form Pd[P(1-naphthyl)(3)](p-C6H4CMe3)[solvent]Br (V) followed by attack of P(o-tolyl)3 to form the mixed bis(phosphine) intermediate Pd[P(o-tol)3][[P(1-naphthyl)(3)](p-C6H4CMe3)Br (VI). Solvolytic displacement of P(o-tolyl)(3) from VI followed by reaction with amine would then form 2.

  DOI：

  10.1021/ic961388v
• 作为产物：
  描述：

  Pd(p-C6H4CMe3)(α,α-benzylamine-d2)2Br * α,α-benzylamine-d2 、 苄胺 生成 Pd(p-C6H4CMe3)(benzylamine)2Br * benzylamine
  参考文献：
  名称：

  Kinetics and Mechanism of the Formation of Palladium Bis(benzylamine) Complexes from Reaction of Benzylamine with Palladium Tri-o-tolylphosphine Mono(amine) Complexes

  摘要：

  The kinetics of the conversion of the palladium mono(benzylamine) complex Pd[P(o-tol)(3)](p-C6H4CMe3)H-2-NBn]Br (2) to the bis(benzylamine) complex Pd(p-C6H4CMe3)[H2NBn](2)Br (3) established the second-order rate law: Rate = k(1)[2][H2NBn], where Delta H-double dagger = 13.8 +/- 0.3 kcal mol(-1) and Delta S-double dagger = -29.7 +/- 0.8 eu. Kinetics were consistent with a mechanism initiated by direct attack of benzylamine on 2 via an associative or interchange mechanism. Benzylamine exchange with both 2 and 3 was > 1.5 x 10(3) times faster than conversion of 2 to 3 under comparable conditions. Complex 2 underwent phosphine exchange in the presence of P(1-naphthyl)(3) to form Pd[P(1-naphthyl)(3)](P-C6H4CMe3)[H2NBn]Br (9). Kinetics of the conversion of 9 to 2 were consistent with associative solvolysis of 9 to form Pd[P(1-naphthyl)(3)](p-C6H4CMe3)[solvent]Br (V) followed by attack of P(o-tolyl)3 to form the mixed bis(phosphine) intermediate Pd[P(o-tol)3][[P(1-naphthyl)(3)](p-C6H4CMe3)Br (VI). Solvolytic displacement of P(o-tolyl)(3) from VI followed by reaction with amine would then form 2.

  DOI：

  10.1021/ic961388v

文献信息

• Formation of Palladium Bis(amine) Complexes from Reaction of Amine with Palladium Tris(<i>o</i>-tolyl)phosphine Mono(amine) Complexes
  作者：Ross A. Widenhoefer、Stephen L. Buchwald

  DOI：10.1021/om9603169

  日期：1996.8.6

  benzylamine in CDCl3 at 25 °C via P(o-tolyl)3 displacement to generate the corresponding bis(amine) derivatives trans-Pd(p-C6H4CMe3)[H2NBn]2X (X = Cl (17), Keq = 0.18 ± 0.02; Br (16), Keq = 0.14 ± 0.01; I (18), Keq = 0.10 ± 0.01). Complexes 16−18 were isolated from reaction of the palladium aryl halide dimers Pd[P(o-tolyl)3](p-C6H4CMe3)(μ-X)}2 (X = Cl (4), Br (5), I (6)) and excess benzylamine as the corresponding

  钯单（苄胺）配合物Pd [P（邻甲苯基）3 ]（p -C 6 H 4 CME 3）[H 2 NBn] X（X = Cl（7），Br（8），I（14））在25°C下通过P（o- tolyl）3置换与苄基胺在CDCl 3中可逆反应，生成相应的双（胺）衍生物反式-Pd（p -C 6 H 4 CME 3）[H 2 NBn] 2 X（ X = Cl（17），Keq = 0.18±0.02; Br（16），K eq = 0.14±0.01; I（18），ķ当量= 0.10±0.01）。配合物16 - 18是从钯的芳基卤化物二聚体PD [P（的反应中分离ö甲苯基）3 ]（p -C 6 H ^ 4 CME 3）（μ-X）} 2（X =氯（4）， Br（5），I（6））和过量的苄胺作为相应的单（苄胺）溶剂化物Pd（p -C 6 H 4 CME 3）[H 2 NBn] 2 X·H 2 NBn（X = Br（16