trans-bis(acetato)bis(triisopropylphosphine)palladium(II) | 545386-12-7

• 分子结构分类: 有机化合物
• 英文名称: trans-bis(acetato)bis(triisopropylphosphine)palladium(II)
• 英文别名: trans-[((i)Pr3P)2Pd(OAc)2]；palladium(2+);tri(propan-2-yl)phosphane;diacetate
• CAS: 545386-12-7
• 化学式: C₂₂H₄₈O₄P₂Pd
• 分子量: 544.988
• InChiKey: DDYLHCINNZBGOB-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  trans-bis(acetato)bis(triisopropylphosphine)palladium(II) 以 二氯甲烷 为溶剂， 生成 cis-[(triisopropylphosphine)Pd(κ2-P,C-P(isopropyl)2CMe2)(pyridine)][B(C6F5)4]
  参考文献：
  名称：

  带有路易斯碱的阳离子钯（II）膦羧酸盐配合物的反应性研究：取代与环金属化

  摘要：

  Two classes of cationic palladium(II) phosphine carboxylate complexes were isolated and characterized. Reactions of trans-[(R3P)(2)Pd(O2CR')(2)] (1) with [Li(OEt2)(2.5)][B(C6F5)(4)] in MeCN led to carboxylate abstraction and formation of trans-[(R3P)(2)Pd(O2CR')(MeCN)][B(C6F5)(4)] (2) in good to excellent yields. On the other hand, carboxylate abstraction reactions of 1 with [Me-2(H)NPh][B(C6F5)(4)] or p-toluenesulfonic acid (HOTs center dot H2O) in CH2Cl2 furnished the palladium cations [(R3P)(2)Pd(kappa(2)-O,O-O2CR')](+) (3). The reactions of 2 and 3 with Lewis bases were found to be different in some cases. For example, reactions of 2 with pyridine furnished the simple products of acetonitrile substitution, trans-[(R3P)(2)Pd(O2CR')(py)][B(C6F5)(4)]. In contrast, the reaction of 3e (R = Pr-i, R' = CH3) with CD3CN in the presence of excess sodium carbonate yielded a material derived from cyclometalation of one of the Pr-i arms of a (Pr3P)-Pr-i ligand. New complexes were characterized by elemental analyses and NMR (H-1, C-13, and P-31) spectroscopic methods and in two cases by single-crystal X-ray structural methods.

  DOI：

  10.1021/om070069g
• 作为产物：
  描述：

  palladium diacetate 、 三异丙基膦 以 二氯甲烷 为溶剂， 反应 2.0h， 以89%的产率得到trans-bis(acetato)bis(triisopropylphosphine)palladium(II)
  参考文献：
  名称：

  Single component cationic palladium proinitiators for the latent polymerization of cycloolefins

  摘要：

  钯化合物组成按照以下公式提供：[((R)3E)aPd(Q)(LB)b]p[WCA]r，其中((R)3E)是第15族电子供体配体，Q是阴离子配体，LB是路易斯碱，WCA是弱配位阴离子，a为1、2或3，b为0、1或2，a和b的总和为1、2或3，p和r各自为整数，使得分子电荷为零，或[(E(R)3)(E(R)2R*)Pd(LB)]p[WCA]r，其中E(R)2R*代表第15族中性电子供体配体，R*是与Pd键合的含有阴离子烃基的部分，并且相对于Pd中心具有β氢。这种化合物组成在多环烯烃存在时表现出潜在的聚合活性。

  公开号：

  US20050187398A1

文献信息

• Synthesis and Reactivity of Cationic Palladium Phosphine Carboxylate Complexes
  作者：Natesan Thirupathi、Dino Amoroso、Andrew Bell、John D. Protasiewicz

  DOI：10.1021/om050356p

  日期：2005.8.1

  Simple routes to two new types of mononuclear cationic palladium phosphine acetate complexes featuring κ1- or κ2-carboxylates have been developed, and the resulting materials have been characterized by single-crystal X-ray diffraction. In acetonitrile the complex [(iPr3P)2Pd(κ2O,O‘-OAc)]+ leads not to the independently prepared trans-[(iPr3P)2Pd(MeCN)(OAc)]+ but to reversible cyclometalation to form

  简单路由到两个新类型的单核的阳离子钯膦配合物醋酸设有κ的1 -或κ 2个-carboxylates被开发出来，并且所得到的材料的特点是单晶X射线衍射。在乙腈络合物[（我镨3 P）2的Pd（κ 2 ø，ö “-OAc）] +引线不将独立制备的反式- [（我镨3 P）2的Pd（MeCN中）（OAC）] +但可逆环金属化以形成[（我镨3 P）（乙腈）钯（κ 2C，P- C（Me）2 P i Pr 2）] +。
• The Impact of Palladium(II) Reduction Pathways on the Structure and Activity of Palladium(0) Catalysts
  作者：Carolyn S. Wei、Geraint H. M. Davies、Omid Soltani、Jacob Albrecht、Qi Gao、Charles Pathirana、Yi Hsiao、Srinivas Tummala、Martin D. Eastgate

  DOI：10.1002/anie.201210252

  日期：2013.5.27

  Two roads diverged: The mechanism of in situ PdII catalyst activation to generate an active LnPd0} catalyst from an air‐stable PdII precursor was examined using the standard conditions of a Miyaura borylation reaction. Two pathways for catalyst activation exist under these conditions, producing two structurally and chemically distinct LnPd0} complexes (see scheme).

  两条道路分歧：使用Miyaura硼化反应的标准条件，研究了原位Pd II催化剂活化从空气稳定的Pd II前体生成活性L n Pd 0 }催化剂的机理。在这些条件下存在两种催化剂活化途径，产生两种结构和化学上不同的L n Pd 0 }配合物（参见方案）。