(1,3-bis(diisopropylphosphino)propane)PdCl2 | 134029-36-0

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: (1,3-bis(diisopropylphosphino)propane)PdCl2
• 英文别名: [(bis(1,3-diisopropylphosphinopropane)))PdCl2]；[PdCl2(di(i-propylphosphino)propane)]；[(dippp)PdCl2]；Dichloropalladium;3-di(propan-2-yl)phosphanylpropyl-di(propan-2-yl)phosphane
• CAS: 134029-36-0
• 化学式: C₁₅H₃₄Cl₂P₂Pd
• 分子量: 453.708
• InChiKey: BUJADYGTOQLKLO-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.35
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (1,3-bis(diisopropylphosphino)propane)PdCl2 以 丙酮 、 甲苯 为溶剂， 生成 {(1,3-bis(diisopropylphosphino)propane)Pd}2(μ-H2)
  参考文献：
  名称：

  Binuclear Palladium Complexes with Bridging Hydrides. Unusual Coordination Behavior of LiBEt4 and NaBEt4

  摘要：

  The reaction of Pd(dippp)Cl-2 (dippp = 1,3-bis(diisopropylphosphino)propane) with a 1:1 mixture of LiBEt(2)H(2) and LiBEt(4) in THF generates the binuclear hydride derivative [(dippp)Pd](2)(mu-H)(2).LiBEt(4) (1) in which the LiBEt(4) is bound to the palladium hydride core. The bare palladium hydride dimer [(dippp)Pd](2)(mu-H)(2) (2) was prepared by reaction of 2 equiv of KBEt(3)H in toluene with Pd(dippp)I-2. Addition of LiBEt(4) to the bare palladium dimer 2 generates the LiBEt(4) adduct 1; this approach has been extended to the preparation of [(dippp)Pd](2)(mu-H)2.NaBEt(4) (3) and [(dippp)Pd](2)(mu-H)(2).LiAlEt(4) (4) by the addition of NaBEt(4) and LiAlEt(4) respectively to 2. On the basis of NMR spectroscopy, there is no evidence for dissociation of the lithium of sodium berate or aluminate salts from the hydride dimer but the ME'Et(4) (M = Li, Na; E' = B, Al) units are labile on the basis of exchange studies and variable temperature NMR data. Crystals of [(dippp)Pd](2)(mu-H)(2).LiBEt(4)0.5(C6H14) (1) are monoclinic, a = 11.537(2) Angstrom, b = 19.114(2) Angstrom, c = 24.020(1) Angstrom, beta = 98.674(9)degrees, Z = 4, space group P2(1)/n; those of [(dippp)Pd](2)(mu-H)(2) (2) are monoclinic, a = 13.128(1) Angstrom, b = 14.362(4) Angstrom, c = 20.353(1) Angstrom, beta = 99.593(6)degrees, Z = 4, space group P2(1)/n; and those of [(dippp)-Pd](2)(mu-H)(2).NaBEt(4) (3) are monoclinic, a = 20.099(2) Angstrom, b = 11.457(5) Angstrom, c = 21.600(3) Angstrom, beta = 92.87(1)degrees, Z = 4, space group P2(1)/c. The structures were solved by the Patterson method and were refined by full-matrix least-squares procedures to R = 0.033, 0.052, and 0.033 (R(W) = 0.029, 0.054, and 0.028) for 5954, 4560, and 5018 reflections with I greater than or equal to 3 sigma(I), respectively. In the solid-state structure of 1, there are three C-H...Li interactions from the ethyl groups attached to boron whereas in the solid-state structure of 3 there are four such C-H...Na interactions.

  DOI：

  10.1021/ja00088a017
• 作为产物：
  描述：

  (1,3-bis(diisopropylphosphino)propane)PdI2 以 二氯甲烷 为溶剂， 生成 (1,3-bis(diisopropylphosphino)propane)PdCl2
  参考文献：
  名称：

  难以捉摸的 (R3P)2MF2(M = Pd, Pt) 配合物的合成

  摘要：

  描述了以前未知的钯 (II) 和铂 (II) 二氟膦配合物的合成和表征。这些配合物可以通过卤化物与 AgF 在二氯甲烷中的复分解反应或通过相应的二甲基配合物与 XeF2 反应获得。虽然 Pt(II) 配合物可以用芳基和烷基膦配体制备，但 Pd(II) 配合物的稳定性仅限于那些具有顺式取向的三烷基膦配体。

  DOI：

  10.1021/ja0377753
• 作为试剂：
  描述：

  甲醇 、 4-氯苯甲醚 、 一氧化碳 在 (1,3-bis(diisopropylphosphino)propane)PdCl2 、 potassium carbonate 作用下， 以 N-甲基吡咯烷酮 为溶剂， 140.0 ℃ 、500.01 kPa 条件下， 反应 24.0h， 以40%的产率得到4-甲氧基苯甲酸甲酯
  参考文献：
  名称：

  芳基卤化物的羰基化：扩大反应范围

  摘要：

  由于羰基中心原子有效地引入醛，酸，酯和酰胺中，羰基化反应在药物化学中越来越受到青睐。简单的芳基碘化物和溴化物的简便方法已得到很好的确立，现在需要开发改进的条件，以使反应扩展至反应性更强的底物，例如位阻化合物和芳基氯化物。空间位阻的化合物如2-碘-或2-溴米-xylenes可使用烷氧基氨基羰基化和被转换，而脱卤成为还原性羰基化的显著副反应。受阻较小的化合物（例如2-碘或溴甲苯）可以成功反应。更改PdCl 2 {Ph 2的芳基配体烷基的P（CH 2）3 PPh 2 }提高了氧化加成速率，但减慢了羰基插入步骤，因此大多数芳基溴化物的速率不会因这种变化而提高。诸如PdCl 2 {Cy 2 P（CH 2）3 PCy 2}为芳基氯化物的烷氧基和氨基羰基化提供更好的性能。然而，对于还原性羰基化而言，脱卤是显着的副反应。CO压力的增加导致催化中间体额外的CO配位并减慢了反应，而脱卤几乎没有受到影响，因此反

  DOI：

  10.1021/op800069w

文献信息

• Catalytic activity of cationic diphospalladium(II) complexes in the alkene/CO copolymerization in organic solvents and water in dependence on the length of the alkyl chain at the phosphine ligands
  作者：Ekkehard Lindner、Markus Schmid、Joachim Wald、Joachim A. Queisser、Michael Geprägs、Peter Wegner、Christiane Nachtigal

  DOI：10.1016/s0022-328x(00)00154-6

  日期：2000.5

  analysis. In particular the water-soluble complexes 2c–k proved to be highly active in the carbon monoxide/ethene copolymerization under biphasic conditions (water–toluene). In the presence of an emulsifier and methanol as activator the catalytic activity increased by a factor of about three. Also higher olefins could be successfully incorporated into the copolymerization with CO and the terpolymerization

  一系列双膦配体CH 2（CH 2 PR 2）2（1a – x）（a – g：R =（CH 2）n OH，n = 1，3-8; h – k：R =（CH 2）n CH（CH 2 OH）2，n = 3–6；l – u：R = C n H 2 n +1，n = 1–8，10，14; v – x：R = CH（CH 3通过相应的1-烯烃的加氢磷酸化反应制备具有不同极性官能团的）2，（CH 2）2 CH（CH 3）2，（CH 2）3 CH（CH 3）2（方案1）。 H 2 P（CH 2）3 PH 2或格氏试剂与Cl 2 P（CH 2）3 PCl 2的反应。水溶性钯络合物[（R 2 P（CH 2）3 PR 2）Pd（OAc）2 ]（2a - k）是通过Pd（OAc）2与配体1a - k在乙醇-乙腈中的反应获得的。用1l – x处理PdCl 2（NCC 6 H 5）2得到二氯钯（II）络合物[（R 2 P（CH
• Unexpected H₂O-Induced Ar−X Activation with Trifluoromethylpalladium(II) Aryls
  作者：Vladimir V. Grushin、William J. Marshall

  DOI：10.1021/ja0602389

  日期：2006.4.1

  is to promote reduction of small quantities of the Pd(II) complex to Pd(0) which activates the Ph-X bond. Subsequent transmetalation to give diphenyl Pd complexes, followed by Ph-Ph reductive elimination give rise to the observed products. The water-induced reduction to catalytically active Pd(0) has been demonstrated to proceed via both the Pd(II)/P(III) to Pd(0)/P(V) redox mechanism and alpha-F transfer

  已经合成了一系列新的配合物 [(LL)Pd(Ar)(CF3)]（LL = dppe、dppp、tmeda；Ar = Ph、p-Tol、C6D5），并在溶液和固态中进行了充分表征。已发现 [(dppe)Pd(Ph)( )] (1) 的显着 Ph-X 活化 (X = I, Cl) 可清洁生产联苯和 [(dppe)Pd(Ph)(X) ]。该反应不会在严格无水的条件下发生，但在存在痕量水的情况下很容易发生，表现出诱导期并且在 PhI 中为零级。机理研究表明，水的作用是促进少量 Pd(II) 络合物还原为 Pd(0)，从而激活 Ph-X 键。随后进行金属转移以得到二苯基钯配合物，然后通过 Ph-Ph 还原消除产生观察到的产物。已证明水诱导还原为具有催化活性的 Pd(0) 是通过 Pd(II)/P(III) 到 Pd(0)/P(V) 氧化还原机制和 α-F 转移进行的，然后是简便的二氟卡宾水解为羰基、迁移插入和还原消除
• 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.
• Portnoy, Moshe; Frolow, Felix; Milstein, David, Organometallics, 1991, vol. 10, # 12, p. 3960 - 3962
  作者：Portnoy, Moshe、Frolow, Felix、Milstein, David

  DOI：——

  日期：——
• Fryzuk, Michael D.; Lloyd, Brian R.; Clentsmith, Guy K. B., Journal of the American Chemical Society, 1991, vol. 113, p. 4332 - 4334
  作者：Fryzuk, Michael D.、Lloyd, Brian R.、Clentsmith, Guy K. B.、Rettig, Steven J.

  DOI：——

  日期：——