(1,2-di(9-phosphabicyclo[3.3.1]nonan-9-yl)ethane)dichloropalladium(II) | 942628-34-4

• 英文名称: (1,2-di(9-phosphabicyclo[3.3.1]nonan-9-yl)ethane)dichloropalladium(II)
• 英文别名: Pd(BCOPE)Cl₂
• CAS: 942628-34-4
• 化学式: C₁₈H₃₂Cl₂P₂Pd
• 分子量: 487.726
• InChiKey: CBWBIOKCGVPIAM-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 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：

  (1,2-di(9-phosphabicyclo[3.3.1]nonan-9-yl)ethane)dichloropalladium(II) 以 二氯甲烷 、 氘代甲醇 为溶剂， 生成
  参考文献：
  名称：

  A para-Hydrogen Investigation of Palladium-Catalyzed Alkyne Hydrogenation

  摘要：

  The complexes [Pd(bcope)(OTf)(2)] (1a), where bcope is (C8H14)PCH2-CH2P(C8H14), and [Pd((t)bucope)(OTf)(2)] (1b), where (t)bucope is (C8H14)PC6H4CH2P(Bu-t)(2), catalyze the conversion of diphenylacetylene to cis- and trans-stilbene and 1,2-diphenylethane. When this reaction was studied with para-hydrogen, the characterization of [Pd(bcope)(CHPhCH2Ph)](OTf) (2a) and [Pd((t)bucope)(CHPhCH2Ph)](OTf) (2b) was achieved. Magnetization transfer from the alpha-H of the CHPhCH2Ph ligands in these species proceeds into trans-stilbene. This process has a rate constant of 0.53 s(-1) at 300 K in methanol-d(4) for 2a, where Delta H-double dagger = 42 +/- 9 kJ mol(-1) and Delta S-double dagger = -107 +/- 31 J mol(-1) K-1, but in CD2Cl2 the corresponding rate constant is 0.18 s(-1), with Delta H-double dagger = 79 +/- 7 kJ mol(-1) and Delta S = 5 +/- 24 J mol(-1) K-1. The analogous process for 2b was too fast to monitor in methanol, but in CD2Cl2 the rate constant for trans-stilbene formation is 1.04 s(-1) at 300 K, with Delta H = 94 +/- 6 kJ mol(-1) and Delta S = 69 +/- 22 J mol(-1) K-1. Magnetization transfer from one of the two inequivalent beta-H sites of the CHPhCH2Ph moiety proceeds into trans-stilbene, while the other site shows transfer into H-2 or, to a lesser extent, cis-stilbene in CD2Cl2, but in methanol it proceeds into the vinyl cations [Pd(bcope)(CPhCHPh)(MeOD)](OTf) (3a) and [Pd((t)bucope)(CPhCHPh)(MeOD)](OTf) (3b). When the same magnetization transfer processes are monitored for 1a in methanol-d(4) containing 5 mu L of pyridine, transfer into trans-stilbene is observed for two sites of the alkyl, but the third proton now becomes a hydride ligand in [Pd(bcope)(H)(pyridine)](OTf) (5a) or a vinyl proton in [Pd(bcope)(CPhCHPh)(pyridine)](OTf) (4a). For 1b, under the same conditions, two isomers of [Pd((t)bucope)(H)(pyridine)](OTf) (5b and 5b') and the neutral dihydride [Pd((t)bucope)(H)(2)] (7) are detected. The single vinylic CH proton in 3 and the hydride ligands in 4 and 5 appear as strong emission signals in the corresponding H-1 NMR spectra.

  DOI：

  10.1021/ja070331c
• 作为产物：
  描述：

  1,2-di(9-phosphabicyclo[3.3.1]nonan-9-yl)ethane 、 dichloro(cycloocta-1,5-diene)palladium (II) 以 二氯甲烷 为溶剂， 生成 (1,2-di(9-phosphabicyclo[3.3.1]nonan-9-yl)ethane)dichloropalladium(II)
  参考文献：
  名称：

  在 Pd 催化的烯烃羰基化反应中使用 Diphobane 配体定向对醛、醇或酯的选择性

  摘要：

  已经合成了具有不同取代基（CF 3、H、OMe、（OMe）2、t Bu）的亚苯基桥连二恶烷配体，并将其用作钯催化的各种烯烃羰基化反应中的配体。已经使用 1-己烯、1-辛烯和戊烯酸甲酯作为底物研究了这些配体在加氢甲酰化与烷氧基羰基化选择性方面的性能，并将结果与​​乙烯桥连二恶烷配体 ( BCOPE ) 进行了比较。1-辛烯在质子溶剂 2-乙基己醇中的加氢甲酰化导致加氢甲酰化和烷氧基羰基化之间的竞争，其中亚苯基桥连的配体，特别是三氟甲基亚苯基桥连的二恶烷L1带有吸电子取代基，通过烷氧基羰基化产生酯产物，而BCOPE通过还原加氢甲酰化产生主要的醇产物（正壬醇和异构体）。在以二甘醇二甲醚为溶剂的 1-己烯的加氢甲酰化中也可以看到BCOPE对还原加氢甲酰化的偏好，生成庚醇作为主要产物，而在这种情况下，亚苯基桥连的配体显示出低得多的活性。亚苯基桥连配体在 1-辛烯甲氧基羰基化生成壬酸甲酯方面表现出优异

  DOI：

  10.1021/acs.organomet.1c00228