[Pd(η3-2-MeC3H4)(piperidine)2](1+) | 160525-03-1

• 英文名称: [Pd(η3-2-MeC3H4)(piperidine)2](1+)
• CAS: 160525-03-1
• 化学式: C₁₄H₂₉N₂Pd
• 分子量: 331.818
• InChiKey: IAQCVDZWJVHYOD-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  哌啶 、 [Pd(η3-2-MeC3H4)(NC5H4(CH=NC6H4OMe-4)-2)]ClO4 以 氯仿 为溶剂， 生成 [Pd(η3-2-MeC3H4)(piperidine)2](1+)
  参考文献：
  名称：

  Equilibrium studies of α-diimine displacement in cationic allylpalladium(II) complexes by monodentate N-donors and the mechanism of allyl amination by triethylamine and pyridine

  摘要：

  In the cationic complexes [Pd(eta3-allyl)(L-L)]ClO4 [L-L = 1,2-bis(imino)ethanes or 2-(iminomethyl)-pyridines] the chelated alpha-diimine was rapidly and reversibly displaced by secondary amines (N-methylaniline, morpholine or piperidine), triethylamine and 4-substituted pyridines. The observed equilibrium constants K(e) increased with increasing basicity and decreasing steric requirements of the entering N-donor. They strongly depend on the alpha-diimine and decrease in the order RN=CHCH=NR much-greater-than RN=C(Me)C(Me)=NR almost-equal-to NC5H4(CH=NR)-2 (R = C6H4OMe-4). The cationic complex [Pd(eta3-C3H5){NC5H4(CH=NC6H4OMe-4)-2}]+ underwent a slow allyl amination by triethylamine or pyridine (L') in the presence of fumaronitrile (fn), yielding [Pd(eta2-fn){NC5H4(CH=NC6H4OMe-4)-2}] and Et3N+CH2CH=CH2 or C5H5N+CH2CH=CH2. Kinetic studies showed that the pseudo-first-order rate constants for amination (k(obs)) are given by k(obs) = k2[L'], suggesting a direct bimolecular attack of L' on the eta3-allyl ligand. Amination hardly proceeds in the presence of the less-activated olefin dimethyl fumarate (dmf). The pi-accepting properties of the olefinic ligands play an important role also in the reaction of Et3N+CH2CH=CH2 or C5H5N+CH2CH=CH2 with [Pd(eta2-olefin){NC5H4(CH=NC6H4OMe-4)-2}] (olefin = fn or dmf), i.e. the reverse of the amination reaction.

  DOI：

  10.1039/dt9940003113