(Ph3As)2Pd

• 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: (Ph3As)2Pd
• 英文别名: Palladium;triphenylarsane
• 化学式: C₃₆H₃₀As₂Pd
• 分子量: 718.897
• InChiKey: IOMYAOJNAXYVBB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  39
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  trans-Ph2Pd2(μ(2)-I)2(AsPh3)2 以 N,N-二甲基甲酰胺 为溶剂， 生成 (Ph3As)2Pd
  参考文献：
  名称：

  Mechanism of the Stille Reaction Catalyzed by Palladium Ligated to Arsine Ligand:  PhPdI(AsPh₃)(DMF) Is the Species Reacting with Vinylstannane in DMF

  摘要：

  The kinetics of the reaction of PhPdl(AsPh3)(2) (formed via the fast oxidative addition of Phi with Pd-0(AsPh3)(2)) with a vinyl stannane CH2=CH-Sn(n-Bu)(3) has been investigated in DMF This reaction (usually called transmetalation step) is the prototype of the rate determining second step of the catalytic cycle of Stille reactions. It is established here that the transmetalation proceeds through PhPdl(AsPh3)(DMF), generated by the dissociation of one ligand AsPh3 from PhPdl(ASPh(3))(2)-PhPdl(AsPh3)(DMF) is the reactive species, which leads to styrene through its reaction with CH2=CH-SnBu3. Consequently, in DMF, the overall nucleophilic attack mainly proceeds via a mechanism involving PhPdl(AsPh3)(DMF) as the central reactive complex and not PhPdl(AsPh3)(2). The dimer [Ph2Pd2(mu(2)-l)(2)(AsPh3)(2)] has been independently synthesized and characterized by its X-ray structure. In DMF, this dimer dissociates quantitatively into PhPd](AsPh3)(DMF), which reacts with CH2=CH-SnBu3. The rate constant for the reaction of PhPdl(AsPh3)(DMF) with CH2=CH-SnBu3 has been determined in DMF for each situation and was found to be comparable.

  DOI：

  10.1021/ja0204978
• 作为试剂：
  描述：

  6-甲基-5-庚烯-2-酮 在 N-甲基吡咯烷酮 、 copper(l) iodide 、 四溴化碳 、 (Ph3As)2Pd 、 双(三甲基硅烷基)氨基钾 、 sodium hydride 、 二异丁基氢化铝 、 三苯基膦 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 50.34h， 生成
  参考文献：
  名称：

  使用碳 13 标记结合溶液和固态 NMR 评估溶液中和蛋白质法呢基转移酶活性位点中的类异戊二烯构象

  摘要：

  酶蛋白法呢基转移酶 (FTase) 使用法呢基二磷酸 (FPP) 作为异戊二烯来源，催化 Ras 蛋白和其他关键信号转导蛋白的法呢基化。因此，FTase 抑制剂作为潜在的新型抗癌剂引起了人们的极大兴趣。此类试剂的设计将通过对 FPP 溶液构象及其在 FTase 活性位点中的构象的详细了解来提供信息。已经合成了四种双 13C 标记的法呢醇和香叶基香叶醇衍生物，并用于制备相应的 FPP 和 GGPP 衍生物。标记的法呢基和香叶基香叶基衍生物 2-7 与溶液 13C NMR 结合使用，以探测各种不同溶剂中异戊二烯链的构象。这些研究，连同分子动力学模拟，证明异戊二烯链主要以扩展构象存在。令人惊讶的是，这种对扩展构象的偏好对溶剂不敏感。没有明显的...

  DOI：

  10.1021/ja000860f

文献信息

• Mechanism of the Stille Reaction. 1. The Transmetalation Step. Coupling of R¹I and R²SnBu₃ Catalyzed by <i>trans</i>-[PdR¹IL₂] (R¹ = C₆Cl₂F₃; R² = Vinyl, 4-Methoxyphenyl; L = AsPh₃)
  作者：Arturo L. Casado、Pablo Espinet

  DOI：10.1021/ja9742388

  日期：1998.9.1

  The so far accepted mechanism of the Stille reaction (palladium-catalyzed cross-coupling of organotin reagents with organic electrophiles) is criticized. Based on kinetic studies on catalytic reactions, and on reactions with isolated intermediates, a corrected mechanism is proposed. The couplings between (RI)-I-1 (1) (R-1 = C-6- Cl2F3 3,5-dichlorotrifluorophenyl) and (RSnBu3)-Sn-2 (R-2 = CH=CH2, 2a; C6H4-4-OCH3, 2b), catalyzed by trans-[(PdRI)-I-1(AsPh3)(2)] (3a), give R-1-R-2 and obey a first-order law, r(obs) = a[3a][2a]/(b + [AsPh3]), with a (2.31 +/- 0.09) x 10(-5) s(-1) and b = (6.9 +/- 0.3) x 10(-4) mol L-1, for [1] [2a] = 0-0.2 mol L-1, [3a] = 0-0.02 mol L-1, and [AsPh3] = 0-0.07 mol L-1, at 322.6 K in THF, The only organopalladium(II) intermediate detected under catalytic conditions is 3a. The apparent activation parameters found for the coupling of 1 with 2a support an associative transmetalation step (Delta H-obs(double dagger) = 50 +/- 2 kJ mol(-1), Delta S-obs(double dagger) = -155 +/- 7 J K-1 mol(-1) in THF; and Delta H-obs(double dagger) = 70.0 +/- 1.7 kJ mol(-1), Delta S-obs(double dagger) = -104 +/- 6 J K-l mol(-1) in chlorobenzene, with [1](0) = [2](0) = 0.2 mol L-1, [3a] = 0.01 mol L-1). The reactions of 2a with isolated trans-[PdR1 X(AsPh3)(2)] (X = halide) show rates Cl > Br > I. From these observations, the following mechanism is proposed: Oxidative addition of (RX)-X-1 to PdLn, gives cis-[(PdRXL2)-X-1], which isomerizes rapidly to trans-[(PdRXL2)-X-1]. This trans complex reacts with the organotin compound following a S-E(2)(cyclic) mechanism, with release of AsPh3 (which explains the retarding effect of the addition of L), to give a bridged intermediate [(PdRL)-L-1(mu-X)(mu-R-2)SnBu3]. In other words, an L-for-R-2 substitution on the palladium leads R-2 and R-1 to mutually cis positions. From there the elimination of XSnBu3 yields a three-coordinate species cis-[(PdRRL)-R-1-L-2], which readily gives the coupling product R-1-R-2.
• Mechanism of the Stille Reaction Catalyzed by Palladium Ligated to Arsine Ligand:  PhPdI(AsPh₃)(DMF) Is the Species Reacting with Vinylstannane in DMF
  作者：Christian Amatore、Ali A. Bahsoun、Anny Jutand、Gilbert Meyer、Alexandre Ndedi Ntepe、Louis Ricard

  DOI：10.1021/ja0204978

  日期：2003.4.1

  The kinetics of the reaction of PhPdl(AsPh3)(2) (formed via the fast oxidative addition of Phi with Pd-0(AsPh3)(2)) with a vinyl stannane CH2=CH-Sn(n-Bu)(3) has been investigated in DMF This reaction (usually called transmetalation step) is the prototype of the rate determining second step of the catalytic cycle of Stille reactions. It is established here that the transmetalation proceeds through PhPdl(AsPh3)(DMF), generated by the dissociation of one ligand AsPh3 from PhPdl(ASPh(3))(2)-PhPdl(AsPh3)(DMF) is the reactive species, which leads to styrene through its reaction with CH2=CH-SnBu3. Consequently, in DMF, the overall nucleophilic attack mainly proceeds via a mechanism involving PhPdl(AsPh3)(DMF) as the central reactive complex and not PhPdl(AsPh3)(2). The dimer [Ph2Pd2(mu(2)-l)(2)(AsPh3)(2)] has been independently synthesized and characterized by its X-ray structure. In DMF, this dimer dissociates quantitatively into PhPd](AsPh3)(DMF), which reacts with CH2=CH-SnBu3. The rate constant for the reaction of PhPdl(AsPh3)(DMF) with CH2=CH-SnBu3 has been determined in DMF for each situation and was found to be comparable.