Pd[κ1-C,κ1-N-C=(C6H5)C(Cl)CH2N(CH3)2](Cl)(pyridine) | 643752-04-9

• 英文名称: Pd[κ1-C,κ1-N-C=(C6H5)C(Cl)CH2N(CH3)2](Cl)(pyridine)
• CAS: 643752-04-9；20492-77-7
• 化学式: C₁₆H₁₈Cl₂N₂Pd
• 分子量: 415.658
• InChiKey: KAQINZTWGITOST-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  N,N-二甲基-3-苯基-2-丙炔-1-胺 以 甲醇 、 二氯甲烷 为溶剂， 生成 Pd[κ1-C,κ1-N-C=(C6H5)C(Cl)CH2N(CH3)2](Cl)(pyridine)
  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

文献信息

• The retro-chloropalladation reaction of heterosubstituted alkynes
  作者：Mara L. Zanini、Mario R. Meneghetti、Gunter Ebeling、Paolo R. Livotto、Frank Rominger、Jairton Dupont

  DOI：10.1016/s0277-5387(03)00324-3

  日期：2003.7

  The bridge-splitting reaction of dimeric palladacycles of the type Pd[kappa(1)-C, kappa(1)-N-C(R) = C(Cl)CH2NMe2](mu-Cl)}(2) (R = Ph, Me, CH2CH2OH), derived from the chloropalladation of propargyl amines (RCdropCCH(2)NMe(2)), with pyridine (Py), triphenylphosphine (PPh3) and tert-butytisonitrile ((BuNC)-Bu-t) affords the monomeric compounds [PdC(R)=CCH2NMe2(Cl)L] (L = Py, PPh3, (BuNC)-Bu-t). These monomeric compounds are not stable in solution and undergo retro-chloropalladation reactions yielding the propargyl amines and [PdCl(L)-mu-Cl](2). This process is strongly dependent upon the nature of the incoming nucleophile (L), the R group on the metallated ligand and the temperature. The retro-halopalladation reaction is almost instantaneous in the case of the reaction of the bromo derivative [PdC(Ph)=C(Br)CH2NMe2-mu-Br](2) and pyridine at room temperature. These results can be rationalized in terms of the stability of the Pd-C bond of the intermediate monomeric compound [PdC(R)=C(X)CH2NMe2(X)L], that is directly related to the nature of its substituents R (Ph, Me and CH2CH2OH), of ligands which are both cis and trans to it (Py, (CNBu)-Bu-t, PPh3, Cl and Br) and the temperature. (C) 2003 Elsevier Science Ltd. All rights reserved.