[Pd(1,2-bis(diisopropylphosphino)ethane)]n | 175693-27-3

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: [Pd(1,2-bis(diisopropylphosphino)ethane)]n
• CAS: 175693-27-3
• 化学式: C₁₄H₃₂P₂*Pd
• 分子量: 368.776
• InChiKey: HYNFNDJTSKNVBB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.58
• 重原子数：
  17.0
• 可旋转键数：
  7.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  [(1,2-(bis-di-isopropylphosphino)ethane)PdCl2] 在 LiHBEt₃ 作用下， 以 四氢呋喃 为溶剂， 生成 [Pd(1,2-bis(diisopropylphosphino)ethane)]n
  参考文献：
  名称：

  The synthesis and structural properties of [M(dippe)(η2-C4H4S)] complexes of Pd and Pt and comparison with their Ni analog

  摘要：

  X-ray structural and NMR spectroscopic data for the ring-opened thiophene complexes [Pd(dippe)(T)] (2), and [Pt(dippe)(T)] (3) are now presented. The complex [Ni(dippe)(T)] (1), where T = (eta(2)-C,S-C4H4S), was reported by our group, previously. The structural and bonding properties of complexes 2 and 3 were compared with those of complex 1. DFT calculations were carried out to rationalize their relative stabilities and structural properties. Compound 1 loses thiophene at ambient temperature in solution, while compound 2 decomposes rapidly in both acetone-d(6) and THF-d(8) with k(obs) = 7.15(9) x 10(-5) and 7.7(3) x 10(-5) s(-1), respectively, to give products that varied by solvent. Complex 3 does not lose thiophene at temperatures below 100 degrees C. The Delta G(0) values determined from DFT calculations are consistent with the observed stabilities of the complexes. The single crystal X-ray structures of all three complexes contain a disordered thienyl fragment in the asymmetric unit due to the interchange of the position of sulfur in the metal-inserted thiophenic ring. The thiophenic moiety is relatively flat in 1, 2 and 3, which is attributed to the open ligand environment at the M(dippe) fragment. All three complexes possess square-planar geometry around the metal center and have bond-length alternation among the thiophenic carbons, which indicates double bond localization. The calculated bond lengths are in good agreement with experimental data. Molecular orbital (MO) and natural bonding orbital (NBO) analyses were carried out to rationalize the results. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2005.10.052
• 作为试剂：
  描述：

  2-甲基乙酰乙酸乙酯 、 间戊二烯 在 [Pd(1,2-bis(diisopropylphosphino)ethane)]n 作用下， 以 四氢呋喃 为溶剂， 反应 60.0h， 以68%的产率得到4-Hexenoic acid, 2-acetyl-2,3-dimethyl-, ethyl ester, (E)-(stereoisomer 1)
  参考文献：
  名称：

  Reaction of 1,3-Dienes with Nucleophiles Catalysed by [1,2-Bis(dialkylphosphino)-ethane] palladium Complexes

  摘要：

  A(η2-丁二烯)[1,2-双(膦基烷基)乙烷]钯复合物在温和条件下催化1,3-二烯与活性氢化合物或醇的反应，生成高产率的1:1加合物。

  DOI：

  10.1055/s-1990-27010

文献信息

• Solution and Solid-State Structures of the Binuclear Zerovalent Palladium Complex [(dippe)Pd]₂(μ-dippe) (dippe = 1,2-Bis(diisopropylphosphino)ethane)
  作者：Michael D. Fryzuk、Guy K. B. Clentsmith、Steven J. Rettig、Gerhard Hägele

  DOI：10.1021/om950825v

  日期：1996.4.16

  The reaction of PdCl2(dippe), where dippe = 1,2-bis(diisopropylphosphino)ethane, with 2 equiv of KBEt(3)H in toluene generates the binuclear palladium(0) derivative [(dippe)Pd](2)(mu-dippe) (4) in 35% yield; alternatively, the reaction of [(eta(3)-C4H7)Pd](2)(mu-Cl)(2) with MeONa in the presence of 3 equiv of dippe generates 4 as well. Mechanistic studies on the attempted formation of mixed binuclear complexes are reported as well as the use of 4 as a catalyst for the reductive dechlorination of chloroarenes. Analysis of the second-order [AB(2)](2) spin system was accomplished by iteration of the 202.47 MHz P-31H-1} NMR spectrum of 4; the solution structure and the solid-state structures are found to be very nearly identical.