trans-[Pd(3,5-dichlorotrifluorophenyl)I(PPh3)2] | 202582-53-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: trans-[Pd(3,5-dichlorotrifluorophenyl)I(PPh3)2]
• 英文别名: trans-[Pd(3,5-C6Cl2F3)I(PPh3)2]；trans-[PdI(PPh3)2(2,4,6-trifluoro-3,5-dichlorophenyl)]；trans-[Pd(C6Cl2F3)I(PPh3)2]
• CAS: 202582-53-4；202667-06-9
• 化学式: C₄₂H₃₀Cl₂F₃IP₂Pd
• 分子量: 957.873
• InChiKey: UGAAJHNEZADUOI-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：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  六甲基磷酰三胺 、 trans-[Pd(3,5-dichlorotrifluorophenyl)I(PPh3)2] 在 PPh₃ 作用下， 以 六甲基磷酰三胺 为溶剂， 生成 trans-[Pd(3,5-C6Cl2F3)(hexamethylphosphoramide)(PPh3)2]I
  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：

  trans-[Pd(3,5-C6Cl2F3)(OTf)(PPh3)2] 以 二氯甲烷 、 丙酮 、 甲苯 为溶剂， 生成 trans-[Pd(3,5-dichlorotrifluorophenyl)I(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
• 作为试剂：
  描述：

  1,3-二氯-2,4,6-三氟-5-碘苯 、 苯基乙炔三丁基锡 在 trans-[Pd(3,5-dichlorotrifluorophenyl)I(PPh3)2] 作用下， 以 四氢呋喃 、 氘代丙酮 为溶剂， 生成 1,3-Dichloro-2,4,6-trifluoro-5-(2-phenylethynyl)benzene
  参考文献：
  名称：

  炔基锡烷与芳基碘化物的斯蒂勒偶联，多途径反应：异构化的重要性

  摘要：

  C 6 Cl 2 F 3 I和PhCCSnBu 3之间的Stille反应动力学已针对整个催化系统和作为单独步骤的重金属化进行了研究。（三氟二氯苯基）钯衍生物的使用减慢了反应的速度，并允许观察到中间体顺式和反式[Pd（C 6 Cl 2 F 3）I（PPh 3）2]。第一个在氧化加成步骤中形成并异构化为第二个。两者均被研究为整个循环的催化剂。动力学研究比较了每种异构体的重金属化步骤的相关性。竞争的金属转移物同时产生顺式和反式-[Pd（C 6 Cl 2 F 3）（PhCC）（PPh 3）2 ]。前者经历了非常快的C-C耦合，而第二者由于极慢的异构化而积累在溶液中。因此，该系统是对Stille反应中竞争途径的影响及其对催化过程性能的影响的案例研究。

  DOI：

  10.1021/om100978w

文献信息

• On the Configuration Resulting from Oxidative Addition of RX to Pd(PPh₃)₄ and the Mechanism of the <i>cis</i>-to-<i>trans</i> Isomerization of [PdRX(PPh₃)₂] Complexes (R = Aryl, X = Halide)
  作者：Arturo L. Casado、Pablo Espinet

  DOI：10.1021/om9709502

  日期：1998.3.1

  isomerization of 2 in THF at 322.6 K reveals a first-order law riso = kiso[2], with kiso = f + g[2]0 + (h + i[2]0)/([PPh3] + j) (f = (1.66 ± 0.03) × 10-4 s-1, g = (2.5 ± 0.2) × 10-3 mol-1 L s-1, h = (1.3 ± 0.7) × 10-8 mol L-1 s-1, i = (4 ± 2) × 10-7 s-1, and j = (1.4 ± 0.7) × 10-5 mol L-1). A four-pathway mechanism accounts for these results:  Two are assigned to the associative replacements of PPh3 coordinated

  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