[Pd[κ1-C,κ1-N-C=(MeO-2-C6H4)C(Cl)CH2NMe2](μ-Cl)]2 | 651729-21-4

• 英文名称: [Pd[κ1-C,κ1-N-C=(MeO-2-C6H4)C(Cl)CH2NMe2](μ-Cl)]2
• CAS: 651729-21-4
• 化学式: C₂₄H₃₀Cl₄N₂O₂Pd₂
• 分子量: 733.166
• InChiKey: WHJFNPROZKRWRT-UHFFFAOYSA-L

反应信息

• 作为反应物：
  描述：

  吡啶 、 [Pd[κ1-C,κ1-N-C=(MeO-2-C6H4)C(Cl)CH2NMe2](μ-Cl)]2 以 二氯甲烷 为溶剂， 以83%的产率得到
  参考文献：
  名称：

  Atropisomerism in palladacycles derived from the chloropalladation of heterosubstituted alkynes

  摘要：

  The chloropalladation of 2-substituted phenyl N,N-propargylamines, Y-2-C6H4C=CCH2NMe2 (1a, Y = H; 2a, Y = CF3; 3a, Y = OMe: 4a. Y = SMe and 5a, Y = NH2) affords palladacycles in different ratios of isomers (geometric and atropisomers). In solution, the parent alkyne (Y = H) and the CF3 substituted derivative generate a mixture of cisoid and transoid chloro-bridged dimer palladacycles of the type {Pd[kappa(1)-C, kappa(1)-N-C=(Y-2-C6H4)C(cl)CH2NMe2](mu-Cl)}(2). Moreover, in the case in the case of Y = CF3 palladacyclic derivative each of the geometric isomers comprises a mixture of two diastereoisomers due to the restricted rotation of the C(vinyl)-C(aryl) sigma bond (atropisomers). Palladacycles 1a (Y = H) and 2a (Y = CF3) crystallize as the single transoid and cisoid-anti isomer. respectively. The OMe substituted alkyne yields a similar dimeric compound that crystallizes as a single cisoid-anti isomer. In solution this dimeric compound is in fast equilibrium with a monomeric pincer compound of the type Pd[kappa(1)-C, kappa(1)-N, kappa(1)-O-C=(MeO-2-C6H4)C(Cl)CH2NMe2](Cl) assisted through the weak coordination of the OMe group. Pincer palladacycles Pd[kappa(1)-C, kappa(1)-N, kappa(1)-Y-C=(Y-2-C6H4)C(Cl)CH2NMe2](Cl) (Y = SMe and NH2) were the sole products obtained in the chloropalladation of alkynes 4a and 5a. The bridge splitting reaction of the dimeric palladacycles 1b-3b with pyridine is highly selective, affording exclusively the corresponding monomeric compounds 1c-3c. The monomeric palladacycle 2d, which comprises a mixture of two atropisomers (2:1 ratio of antilsyn) was obtained from the reaction of 2b with 2-methylpyridine. Theoretical calculations indicated that the anti isomer of 2d is 5.42 kJ mol(-1) more stable than its syn isomer. (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(03)00011-2
• 作为产物：
  描述：

  palladium dichloride 、 lithium chloride 、 1-[2-(methoxy)-phenyl]-3-(dimethytlamino)-1-propyne 以 甲醇 为溶剂， 以51%的产率得到[Pd[κ1-C,κ1-N-C=(MeO-2-C6H4)C(Cl)CH2NMe2](μ-Cl)]2
  参考文献：
  名称：

  Atropisomerism in palladacycles derived from the chloropalladation of heterosubstituted alkynes

  摘要：

  The chloropalladation of 2-substituted phenyl N,N-propargylamines, Y-2-C6H4C=CCH2NMe2 (1a, Y = H; 2a, Y = CF3; 3a, Y = OMe: 4a. Y = SMe and 5a, Y = NH2) affords palladacycles in different ratios of isomers (geometric and atropisomers). In solution, the parent alkyne (Y = H) and the CF3 substituted derivative generate a mixture of cisoid and transoid chloro-bridged dimer palladacycles of the type {Pd[kappa(1)-C, kappa(1)-N-C=(Y-2-C6H4)C(cl)CH2NMe2](mu-Cl)}(2). Moreover, in the case in the case of Y = CF3 palladacyclic derivative each of the geometric isomers comprises a mixture of two diastereoisomers due to the restricted rotation of the C(vinyl)-C(aryl) sigma bond (atropisomers). Palladacycles 1a (Y = H) and 2a (Y = CF3) crystallize as the single transoid and cisoid-anti isomer. respectively. The OMe substituted alkyne yields a similar dimeric compound that crystallizes as a single cisoid-anti isomer. In solution this dimeric compound is in fast equilibrium with a monomeric pincer compound of the type Pd[kappa(1)-C, kappa(1)-N, kappa(1)-O-C=(MeO-2-C6H4)C(Cl)CH2NMe2](Cl) assisted through the weak coordination of the OMe group. Pincer palladacycles Pd[kappa(1)-C, kappa(1)-N, kappa(1)-Y-C=(Y-2-C6H4)C(Cl)CH2NMe2](Cl) (Y = SMe and NH2) were the sole products obtained in the chloropalladation of alkynes 4a and 5a. The bridge splitting reaction of the dimeric palladacycles 1b-3b with pyridine is highly selective, affording exclusively the corresponding monomeric compounds 1c-3c. The monomeric palladacycle 2d, which comprises a mixture of two atropisomers (2:1 ratio of antilsyn) was obtained from the reaction of 2b with 2-methylpyridine. Theoretical calculations indicated that the anti isomer of 2d is 5.42 kJ mol(-1) more stable than its syn isomer. (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(03)00011-2