| 327596-90-7

• CAS: 327596-90-7
• 化学式: C₁₇H₃₄O₂P₂Pd
• 分子量: 438.823
• InChiKey: MMHBWUBSBRBJEG-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：

  以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Synthesis, Characterization, and Reactivity of [((ⁱPr)₂P(CH₂)₃P(ⁱPr)₂)(PCy₃)PdH][OR]

  摘要：

  The preparation of (DIPPP)Pd(PR3) and [(DIPPP)(PR3)PdH][OR'] (DIPPP = bis(1,3-diisopropylphosphino)propane; R = Cy, Et; R' = Ar, CF3SO2) is reported. (DIPPP)Pd(PCy3) and [(DIPPP)(PCy3)PdH][CF3SO3] have been structurally characterized. (DIPPP)Pd(PR3) complexes catalyze the reaction of ethylene with carbon monoxide and phenols to give aryl propionates. In situ P-31 NMR experiments have shown that the resting state of the catalyst in these transformations is the binuclear species [C(DIPPP)Pd)(2)(mu -H)(mu -CO)][OPh].

  DOI：

  10.1021/om0008833
• 作为产物：
  描述：

  3-di(propan-2-yl)phosphanylpropyl-di(propan-2-yl)phosphane;palladium;triethylphosphane 生成
  参考文献：
  名称：

  Synthesis, Characterization, and Reactivity of [((ⁱPr)₂P(CH₂)₃P(ⁱPr)₂)(PCy₃)PdH][OR]

  摘要：

  The preparation of (DIPPP)Pd(PR3) and [(DIPPP)(PR3)PdH][OR'] (DIPPP = bis(1,3-diisopropylphosphino)propane; R = Cy, Et; R' = Ar, CF3SO2) is reported. (DIPPP)Pd(PCy3) and [(DIPPP)(PCy3)PdH][CF3SO3] have been structurally characterized. (DIPPP)Pd(PR3) complexes catalyze the reaction of ethylene with carbon monoxide and phenols to give aryl propionates. In situ P-31 NMR experiments have shown that the resting state of the catalyst in these transformations is the binuclear species [C(DIPPP)Pd)(2)(mu -H)(mu -CO)][OPh].

  DOI：

  10.1021/om0008833

文献信息

• A binuclear palladium(I) hydride. Formation, reactions, and catalysis
  作者：Moshe Portnoy、David Milstein

  DOI：10.1021/om00014a035

  日期：1994.2

  (dippp)Pd(Ph)Cl (3) reacts with methanol to yield the novel hydrido Pd(I) dimer [(dippp)-Pd]2(mu-H)(mu-CO)}+Cl- (1), (dippp)PdCl2 (4), H-2, benzene, and formaldehyde. In the presence of NEt3, HNEt3+Cl- is formed instead of 4. 1 can also be formed in a reaction of Pd(diPPP)2, HCl, and CO. Labeling studies and modeling reactions indicate that the novel transformation of 3 into 1 involves methanolysis of 3 followed by a beta-H elimination from a methoxo intermediate to yield formaldehyde, benzene, and the 14e transient (dippp)Pd (7). Formaldehyde decarbonylation, coupling of the palladium carbonyl complex with 7, and protonation lead to 1. Alternatively, 1 can be formed by electrophilic attack of protonated 7, on the carbonyl complex (dippp)Pd(CO). A number of reactivity modes have been identified for 1. Reaction with acetylenes results in bridge-splitting to form (dippp)Pd(eta2-acetylene) and in hydropalladation of the acetylene to form a vinyl complex. The hydropalladation process exhibits high regio- and stereoselectivity, resulting in cis addition and attachment of the Pd atom to the more hindered carbon, indicating electronic control. 1 undergoes exchange of the hydride for deuteride in CD3COCD3, most likely via an enol insertion into Pd-H. In the presence of an olefin, such as cyclooctene or ethyl vinyl ether, catalytic transfer deuteration takes place. Alpha-deuteration of the latter is preferred, indicating anti-Markovnikov Pd-H addition. The integrity of 1 is maintained during this process. With norbornene, bridge-splitting to form (dippp)Pd(norbornyl) (17) and its CO-insertion product 18 takes place. No H/D exchange catalysis is observed in this case with acetone-d6. 1 behaves as a Pd(0) complex and exhibits oxidative addition reactivity with chlorobenzene or benzylchloride, yielding (dippp)Pd(R)Cl. The relevance of this reactivity to Pd-catalyzed reactions is discussed.