palladium(2+);2-phenylethenylbenzene;triethylphosphane;acetate | 1338056-14-6

• 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: palladium(2+);2-phenylethenylbenzene;triethylphosphane;acetate
• CAS: 1338056-14-6
• 化学式: C₂₈H₄₄O₂P₂Pd
• 分子量: 581.024
• InChiKey: PFKXQHGHNLCYOY-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  7.36
• 重原子数：
  33
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  40.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  palladium(2+);2-phenylethenylbenzene;triethylphosphane;acetate 在 二乙基硅烷 作用下， 反应 96.0h， 以50%的产率得到
  参考文献：
  名称：

  Identification of Alkenyl- and Arylpalladium Hydrides with the Aid of Hydrosilanes

  摘要：

  通过用氢化硅烷还原钯醋酸盐，再用氢化硅烷稳定氢化钯，首次分离出了长期以来提出的热力学不稳定催化中间体烯基和芳基配合物 sp2C-Pd-H。通过 X 射线分析确定了这些氢ridopalladium 的结构。

  DOI：

  10.1246/cl.130588
• 作为产物：
  描述：

  二苯乙烯 以 氘代苯 为溶剂， 反应 77.0h， 生成 palladium(2+);2-phenylethenylbenzene;triethylphosphane;acetate
  参考文献：
  名称：

  Identification of Alkenyl- and Arylpalladium Hydrides with the Aid of Hydrosilanes

  摘要：

  通过用氢化硅烷还原钯醋酸盐，再用氢化硅烷稳定氢化钯，首次分离出了长期以来提出的热力学不稳定催化中间体烯基和芳基配合物 sp2C-Pd-H。通过 X 射线分析确定了这些氢ridopalladium 的结构。

  DOI：

  10.1246/cl.130588

文献信息

• Facile Regio- and Stereoselective Hydrometalation of Alkynes with a Combination of Carboxylic Acids and Group 10 Transition Metal Complexes: Selective Hydrogenation of Alkynes with Formic Acid
  作者：Ruwei Shen、Tieqiao Chen、Yalei Zhao、Renhua Qiu、Yongbo Zhou、Shuangfeng Yin、Xiangbo Wang、Midori Goto、Li-Biao Han

  DOI：10.1021/ja2069246

  日期：2011.10.26

  highly stereo- and regioselective hydrometalation of alkynes generating alkenylmetal complex is disclosed for the first time from a reaction of alkyne, carboxylic acid, and a zerovalent group 10 transition metal complex M(PEt(3))(4) (M = Ni, Pd, Pt). A mechanistic study showed that the hydrometalation does not proceed via the reaction of alkyne with a hydridometal generated by the protonation of a

  通过炔烃、羧酸和零价族 10 过渡金属络合物 M(PEt(3))(4) (M =镍、钯、铂）。一项机理研究表明，氢金属化不是通过炔烃与由羧酸与 Pt(PEt(3))(4) 质子化产生的氢化金属反应进行的，而是通过炔烃配位金属络合物与酸。这一发现阐明了长期以来提出的反应机制，该机制通过生成烯基钯中间体和随后在由 Brφnsted 酸和 Pd(0) 配合物的组合催化的各种反应中转化该配合物来进行。
• Highly Selective Markovnikov Addition of Hypervalent<i>H</i>-Spirophosphoranes to Alkynes Mediated by Palladium Acetate: Generality and Mechanism
  作者：Li-Biao Han、Yutaka Ono、Qing Xu、Shigeru Shimada

  DOI：10.1246/bcsj.20100141

  日期：2010.9.15

  Palladium acetate efficiently catalyzes the addition of an H-spirophosphorane (pinacolato)2PH to alkynes to give Markovnikov addition products highly selectively. The addition products can be easily converted to the corresponding alkenylphosphonates and phosphonic acids via simple hydrolysis or thermal decomposition. This new reaction is a general method for the introduction of phosphorus functionality to the internal carbons of terminal alkynes, resolving the problem of the regioselectivity associated with hydrophosphorylation reactions so far reported. Mechanistic studies confirmed that (a) palladium acetate was reduced to metallic palladium by H-spirophosphorane, (b) the P–H bond of H-spirophosphorane could be activated by zero-valent platinum complexes to give the corresponding hydridoplatinum complexes, and (c) an alkenylpalladium species was identified from the reaction of palladium acetate with H-spirophosphorane and diphenylacetylene. These results support a reaction mechanism that palladium acetate was first reduced by H-spirophosphorane to give zero-valent palladium. This zero-valent palladium might insert into the P–H bond of the H-spirophosphorane to give a hydridopalladium species which then added to alkyne via the addition of H–Pd bond to form an alkenylpalladium species with the hydrogen atom added to the terminal carbon of alkynes. Reductive elimination of the alkenylpalladium affords the addition product.

  乙酸钯能高效催化H-螺磷烷（pinacolato）2PH与炔烃反应,高选择性地得到马氏加成产物。该加成产物通过简单的水解或热分解即可转化为相应的烯基膦酸盐和膦酸。这一新反应为解决端炔的内碳原子亲核膦化反应的区域选择性问题提供了一般性的方法。机理研究表明：（a）乙酸钯被H-螺磷烷还原为金属钯;（b）零价铂配合物可活化H-螺磷烷的P-H键,生成相应的氢铂配合物;（c）乙酸钯与H-螺磷烷和二苯基乙炔反应生成了烯基钯物种。这些结果支持下列反应机理：乙酸钯首先被H-螺磷烷还原为零价钯,后者插入H-螺磷烷的P-H键生成氢钯物种,该氢钯物种与炔烃反应时, H-Pd键加成形成烯基钯物种,其中的氢原子加成到炔烃的末端碳原子上,最后经还原消除生成加成产物。