(4-(trifluoromethyl)phenyl)Pd(P(C6H5)3)2I | 84206-28-0

• 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: (4-(trifluoromethyl)phenyl)Pd(P(C6H5)3)2I
• 英文别名: Iodopalladium(1+);trifluoromethylbenzene;triphenylphosphane
• CAS: 84206-28-0
• 化学式: C₄₃H₃₄F₃IP₂Pd
• 分子量: 903.01
• InChiKey: LMEUYUCQRDTQKQ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  10.28
• 重原子数：
  50
• 可旋转键数：
  6
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.02
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4-(trifluoromethyl)phenyl)Pd(P(C6H5)3)2I 以 氘代氯仿 为溶剂， 以0%的产率得到
  参考文献：
  名称：

  Mechanistic Studies on the Aryl−Aryl Interchange Reaction of ArPdL₂I (L = Triarylphosphine) Complexes

  摘要：

  The aryl-aryl interchange reaction of ArPdL2I complex Im was found to follow pseudo-first-order kinetics. A marked inhibition in the presence of excess phosphine and/or excess iodide was observed, suggesting that a dissociative pathway was involved, contrary to the analogous alkyl-aryl interchange reaction studied previously. Phosphine flooding experiments could not be performed due to a competing phosphonium salt formation reaction that occurred in the presence of excess phosphine. A deuterium labeling experiment indicated that the interchange reaction proceeded via the reductive elimination to form the phosphonium salt, suggesting that excess phosphine was acting as a trap for intermediate palladium(0) species preventing the generation of the interchanged palladium(II) complex. Substituent effect studies of the interchange reaction indicated that it was inhibited by electron-withdrawing groups on both the phosphine and palladium-bound aryl groups and by increased steric bulk on both the phosphine and palladium-bound aryl groups. Under catalytic conditions, the distribution of phosphines formed from the aryl-aryl interchange during palladium-mediated cross-coupling reactions could be modeled by statistics. Various strategies for eliminating the formation of byproducts caused by the interchange during cross-coupling reactions were screened and optimized.

  DOI：

  10.1021/ja972554g
• 作为产物：
  描述：

  四(三苯基膦)钯 、 4-碘三氟甲苯 以 四氢呋喃 为溶剂， 反应 6.0h， 以45%的产率得到(4-(trifluoromethyl)phenyl)Pd(P(C6H5)3)2I
  参考文献：
  名称：

  有机化合物活化降冰片烯衍生物进行乙烯基加成聚合的钯前催化剂

  摘要：

  已经开发了一种不使用添加剂例如路易斯酸来活化Pd-络合物的方法，用于降冰片烯的加成聚合。有效地将芳基碘化物和芳基重氮盐用作Pd（0）-和Pd（2 +）-络合物的助催化剂。所开发的系统在惰性气氛和空气中催化了含有大体积和极性官能团的降冰片烯的聚合反应，从而生成了可溶且高分子量的饱和聚合物。

  DOI：

  10.1039/d1cc00546d

文献信息

• New Methods for the Synthesis of ArPdL₂I (L = Tertiary Phosphine) Complexes
  作者：Thomas I. Wallow、Felix E. Goodson、Bruce M. Novak

  DOI：10.1021/om9602567

  日期：1996.8.20

  Organopalladium ArPdL2I (L = tertiary phosphine) complexes (1) can be synthesized in one step from the precursors Pd2(dba)3·C6H6 (2) (dba = t,t-dibenzylideneacetone) and (η3-allyl)PdCp (3) (Cp = η5-cyclopentadienide). Two advantages over previous synthetic methods are that this route requires only stoichiometric amounts of phosphine and that the desired complexes are easily isolated from reaction byproducts

  有机钯ArPdL 2 I（L =叔膦）配合物（1）可在从所述前体的Pd一个步骤中合成2（DBA）3 ·C 6 H ^ 6（2）（DBA =吨，吨-dibenzylideneacetone）和（η 3 -烯丙基）PDCP（3）（CP =η 5-环戊二烯）。与以前的合成方法相比，有两个优点是该路线仅需要化学计量的膦，而且所需的络合物很容易从反应副产物中分离出来。研究了这些反应的范围和一般性，并讨论了使用这种方法合成许多新的有机和水溶性配合物。改进了水溶性配体P（C 6 H 5）2（4-SO 3 KC 6 H 4）（5）和As（C 6 H 5）2（4-SO 3 KC 6 H 4）（6）的合成）。
• In Situ Generation of ArCu from CuF₂ Makes Coupling of Bulky Aryl Silanes Feasible and Highly Efficient
  作者：Juan delPozo、Juan A. Casares、Pablo Espinet

  DOI：10.1002/chem.201504435

  日期：2016.3.14

  fairly hindered aryl silanes with aryl, anisyl, phenylaldehyde, p‐cyanophenyl, p‐nitrophenyl, or pyridyl iodides of conventional size. The reaction involves the activation of the silane by CuII, followed by disproportionation and transmetalation from the CuI(aryl) to PdII, upon which coupling takes place. CuIII formed during disproportionation is reduced to CuI(aryl) by excess aryl silane, so that

  Pd / CuF 2的双金属体系（在Pd中催化而在Cu中以化学计量）非常有效且具有选择性，可将相当受阻的芳基硅烷与传统的芳基，茴香基，苯甲醛，对氰基苯基，对硝基苯基或吡啶基碘化物偶联尺寸。该反应包括通过Cu II活化硅烷，然后发生歧化和从Cu I（芳基）到Pd II的重金属转移，然后发生偶联。歧化过程中形成的Cu III被过量的芳基硅烷还原为Cu I（芳基），因此CuF 2体系被完全转化为Cu I（芳基）并用于偶联。此外，不需要额外的氟化物源。在受阻芳基硅烷的竞争反应中发现了对偶联的有趣的尺寸选择性。到目前为止，易于获得的[PdCl 2（IDM）（AsPh 3）]（IDM = 1,3-二甲基咪唑-2-亚烷基）是最好的催化剂，分离出的产物基本上不含As或Pd（<1 ppm）。该过程的机械方面已通过实验检查和讨论。