trans-[Pd(3,5-dichlorotrifluorophenyl)Cl(PPh3)2] | 202582-55-6

• 英文名称: trans-[Pd(3,5-dichlorotrifluorophenyl)Cl(PPh3)2]
• 英文别名: trans-[Pd(3,5-C6Cl2F3)Cl(PPh3)2]；trans-[PdCl(C₆Cl₂F₃)(PPh₃)₂]；trans-[Pd(3,5-dichloro-2,4,6-trifluorophenyl)Cl(PPh3)2]
• CAS: 202582-55-6
• 化学式: C₄₂H₃₀Cl₃F₃P₂Pd
• 分子量: 866.422
• InChiKey: DBGSLZBQYSMZJR-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：

  trans-[Pd(3,5-dichlorotrifluorophenyl)Cl(PPh3)2] 以 二氯甲烷 、 丙酮 为溶剂， 生成 trans-[Pd(3,5-C6Cl2F3)(CH=CH2)(PPh3)2]
  参考文献：
  名称：

  Mechanism of the Stille Reaction. 2. Couplings of Aryl Triflates with Vinyltributyltin. Observation of Intermediates. A More Comprehensive Scheme

  摘要：

  The mechanism of the [PdL4]-catalyzed couplings between R-OTf (R = pentahalophenyl; L = PPh3, AsPh3) and Sn(CH=CH2)Bu-3 has been studied. The addition of LiCl favors the coupling for L = AsPh3 in THF but retards it for L = PPh3. Separate experiments show that for L = AsPhs, LiCl accelerates the otherwise very slow and rate-determining oxidative addition of the aryl triflate to [PdL4], leading to trans[PdRClL2]. Therefore, the overall process is accelerated. For L = PPh3, the rate-determining step is the transmetalation. Complex trans-[PdRXL2],with X = Cl, is formed in the presence of LiCl, whereas an equilibrium mixture mainly involving species with X = TfO, L, or S (S = solvent) is established in the absence of LiCl. Since the transmetalation is slower for X = Cl than for the other complexes, the overall process is retarded by addition of LiCl. The transmetalation in complexes trans-[PdRXL2], with X = Cl, follows the S(E)2(cyclic) mechanism proposed in Part 1 (Casado, A. L.; Espinet, P. J. Am. Chem. Sec. 1998, 120, 8978-8985), giving the coupling product R-CH=CH2 directly. For X = TfO or, L rather stable intermediates trans[PdR(CH=CH2)L-2] are detected, Supporting an SE2(open) mechanism. The I;ey:intermediates undergoing transmetalation in the conditions arid solvents most commonly used in the literature have been identified.;The operation of S(E)2(cyclic) and S(E)2(open) pathways emphasizes common aspects of the Stille reaction with the Hiyama reaction where, using (RSiF3)-Si-2 that is chiral at the alpha -carbon of R retention or inversion gt the transmetalated chiral carbon can be-induced. This helps us to understand the contradictory stereochemical outcomes in the literature for Stille couplings using (RSnR3)-Sn-2 derivatives that are chiral Bt the a-carbon of R-2 and suggests that stereocontrol of the Stille reaction might be achieved.

  DOI：

  10.1021/ja001511o
• 作为产物：
  描述：

  三苯基膦 、 anti-(μ-Cl)₂-[Pd₂(C₆Cl₂F₃)₂(tht)₂] 以 丙酮 为溶剂， 以96%的产率得到trans-[Pd(3,5-dichlorotrifluorophenyl)Cl(PPh3)2]
  参考文献：
  名称：

  在配置从RX的氧化加成到的Pd（PPh所得3）4和机理的顺式-到-反式的异构化[PdRX（PPH 3）2 ]配合物（R =芳基，X =卤化物）†

  摘要：

  氧化加成RI与Pd（0），并进一步顺-到-反式异构化，其涉及在Stille反应等钯催化合成，进行了研究。在室温下，将C 6 Cl 2 F 3 I（1，C 6 Cl 2 F 3 = 3,5-二氯三氟苯基）加到Pd（PPh 3）4的THF中，得到顺式-[Pd（C 6 Cl 2 F 3）I （PPh 3）2 ]（2），可以在异构化之前分离为更稳定的反式-[Pd（C 6 Cl 2 F 3）I（PPh 3）2 ]（3）。甲19的异构化的F NMR动力学研究2在THF中在322.6ķ揭示了一阶法ř异= ķ异丙[ 2 ]，其中ķ异= ˚F +克[ 2 ] 0 +（ħ +我[ 2 ] 0）/（[[PPh 3 ] + j）（f=（1.66±0.03）×10 - 4个小号- 1，克=（2.5±0.2）×10 - 3摩尔- 1大号小号- 1，ħ =（1.3±0.7）×10 - 8摩尔大号- 1个小号- 1，我=（4±2）×10

  DOI：

  10.1021/om9709502

文献信息

• Experimental study of the [ZnCl2(THF)2] catalyzed cis/trans-isomerization of [Pd(C6Cl2F3)Me(PPh3)2] and of the transmetalation of trans-[PdCl(C6Cl2F3)(PPh3)2] with [ZnMeCl(THF)2]
  作者：Desiré Carrasco、Juan A. Casares

  DOI：10.1016/j.ica.2020.120206

  日期：2021.3
• Insights into the Mechanism of the Negishi Reaction:  ZnRX versus ZnR₂ Reagents
  作者：Juan A. Casares、Pablo Espinet、Beatriz Fuentes、Gorka Salas

  DOI：10.1021/ja070235b

  日期：2007.3.1

  The observation that their transmetalations with trans-[PdRfCl(PPh3)(2)] (Rf = fluoroaryl) give stereoselectively a different isomer of [PdRfMe(PPh3)(2)] suggests that Negishi reactions with ZnRX or ZnR2 could show very different evolutions.