(iPr3P)Pd(η3-C3H5)(η1-C3H5) | 344927-00-0

• 英文名称: (iPr3P)Pd(η3-C3H5)(η1-C3H5)
• CAS: 344927-00-0
• 化学式: C₁₅H₃₁PPd
• 分子量: 348.805
• InChiKey: FTMOLHSZUTXLDY-UHFFFAOYSA-N

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：

  (iPr3P)Pd(η3-C3H5)(η1-C3H5) 以 neat (no solvent) 为溶剂， 生成 ((iPr3P)Pd)2(μ-C3H5)2
  参考文献：
  名称：

  A Dinuclear Palladium(I) Ethynyl Complex:  Synthesis, Structure, and Dynamics

  摘要：

  The reaction of Pd(eta (3)-C3H5)(2) with (PPr3)-Pr-i at -30 degreesC affords yellow crystals of the Pd-II complex ((Pr3P)-Pr-i)Pd(eta (3)-C3H5)(eta (3)-C3H5) (1). At 20 degreesC 1 transforms into the dinuclear Pd-I complex {((Pr3P)-Pr-i)Pd)(2)(mu -C3H5)(2) (2) due to oxidative C-C coupling of two allyl groups with elimination of 1,5-hexadiene. Heating 1 or 2 in 1,6-heptadiene to 80 degreesC produces the Pd-0 complex ((Pr3P)-Pr-i)Pd(eta (2),eta (2)-C7H12) (3) {(eta (3)-C3H5)PdCl}(2) reacts with (Pr3P)-Pr-i to give ((Pr3P)-Pr-i)Pd(eta (3)-C3H5)Cl (4b), from which further derivatives ((Pr3P)-Pr-i)Pd(eta (3)-C3H5)X (X = OSO2CF3 (4a), C drop CH (5a), CH3 (5b)) are obtained by replacement reactions. The mononuclear Pd-II-acetylide Sa and complex 3 combine to give the dinuclear Pd-I derivative {((Pr3P)-Pr-i)Pd}(2)(mu -C3H5)(mu (2)-eta (2)-C2H) (6). The Pd-Pd bond in 6 is unsymmetrically bridged by a pi -allyl and a sigma-pi -ethynyl group, as determined by X-ray structure analysis. The structures of 1, 4a,b, and 6 are dynamic in solution, with 1 undergoing an exchange of the binding modes of the pi- and sigma -coordinated allyl groups and 4a,b displaying a pi/sigma -allyl group rearrangement, and in 6 the C drop CH substituent oscillates in its pi -coordination from one Pd-I atom to the other.

  DOI：

  10.1021/om000765f
• 作为产物：
  描述：

  bis(η³-allyl)palladium 、 三异丙基膦 以 乙醚 为溶剂， 以60%的产率得到(iPr3P)Pd(η3-C3H5)(η1-C3H5)
  参考文献：
  名称：

  A Dinuclear Palladium(I) Ethynyl Complex:  Synthesis, Structure, and Dynamics

  摘要：

  The reaction of Pd(eta (3)-C3H5)(2) with (PPr3)-Pr-i at -30 degreesC affords yellow crystals of the Pd-II complex ((Pr3P)-Pr-i)Pd(eta (3)-C3H5)(eta (3)-C3H5) (1). At 20 degreesC 1 transforms into the dinuclear Pd-I complex {((Pr3P)-Pr-i)Pd)(2)(mu -C3H5)(2) (2) due to oxidative C-C coupling of two allyl groups with elimination of 1,5-hexadiene. Heating 1 or 2 in 1,6-heptadiene to 80 degreesC produces the Pd-0 complex ((Pr3P)-Pr-i)Pd(eta (2),eta (2)-C7H12) (3) {(eta (3)-C3H5)PdCl}(2) reacts with (Pr3P)-Pr-i to give ((Pr3P)-Pr-i)Pd(eta (3)-C3H5)Cl (4b), from which further derivatives ((Pr3P)-Pr-i)Pd(eta (3)-C3H5)X (X = OSO2CF3 (4a), C drop CH (5a), CH3 (5b)) are obtained by replacement reactions. The mononuclear Pd-II-acetylide Sa and complex 3 combine to give the dinuclear Pd-I derivative {((Pr3P)-Pr-i)Pd}(2)(mu -C3H5)(mu (2)-eta (2)-C2H) (6). The Pd-Pd bond in 6 is unsymmetrically bridged by a pi -allyl and a sigma-pi -ethynyl group, as determined by X-ray structure analysis. The structures of 1, 4a,b, and 6 are dynamic in solution, with 1 undergoing an exchange of the binding modes of the pi- and sigma -coordinated allyl groups and 4a,b displaying a pi/sigma -allyl group rearrangement, and in 6 the C drop CH substituent oscillates in its pi -coordination from one Pd-I atom to the other.

  DOI：

  10.1021/om000765f