bis(1,3-bis(diphenylphosphino)-2,2-dimethylpropane)palladium | 125611-29-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis(1,3-bis(diphenylphosphino)-2,2-dimethylpropane)palladium
• 英文别名: Pd(L3X)2
• CAS: 125611-29-2
• 化学式: C₅₈H₆₀P₄Pd
• 分子量: 987.429
• InChiKey: SKVQELCEUGDHRQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.55
• 重原子数：
  63.0
• 可旋转键数：
  8.0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  (2,2-dimethylpropane-1,3-diyl)bis(diphenylphosphane) 在 KF 、 18-crown-6 作用下， 以 四氢呋喃 、 吡啶 、 苯 为溶剂， 生成 bis(1,3-bis(diphenylphosphino)-2,2-dimethylpropane)palladium
  参考文献：
  名称：

  氟化物诱导的钯（II）和铂（II）膦配合物的还原

  摘要：

  A novel redox reaction involving fluoride and phosphine complexes of palladium(II) is reported. The scope of this reaction has been investigated using the ligands PPh3, Ph2P(CH2)nPPh2 (n = 1-4), Ph2PCH2C(CH3)2CH2PPh2, Ph2PCH3, and P(CH2CH2CN)3; several solvents including DMSO, pyridine, acetonitrile, and THF; and either n-Bu4NF.3H2O or KF/18-crown-6 as the fluoride source. The reduction products are palladium(0) phosphine complexes for which this reaction offers a convenient synthetic route. P-31 and F-19 NMR spectra permitted identification of the initial oxidation products as difluorophosphoranes (R3PF2), which subsequently hydrolyzed, forming phosphine oxides if a hydrated fluoride source is used. Results implicating a fluoride-induced redox reaction in the thermal decomposition of [(Ph3P)3PdCl]BF4 to yield [Pd3Cl(PPh2)2(PPh3)3] BF4 are also presented. Preliminary results indicate that platinum complexes also undergo this reaction, but nickel complexes yield NiF2. The X-ray parameters for Pd(dppp)2 (dppp = 1,3-bis(diphenyphosphino)propane) are: monoclinic, space group C2/c (No. 15), a = 18.396 (2) angstrom, b = 13.290 (1) angstrom, c = 20.186 (2) angstrom, beta = 109.383 (5)-degrees, and Z = 4.

  DOI：

  10.1021/om00042a040

文献信息

• Reductive Elimination from Arylpalladium Cyanide Complexes
  作者：Jessica L. Klinkenberg、John F. Hartwig

  DOI：10.1021/ja300827t

  日期：2012.4.4

  and characterization of arylpalladium cyanide complexes that undergo reductive elimination to form arylnitriles. The rates of reductive elimination from a series of arylpalladium cyanide complexes reveal that the electronic effects on the reductive elimination from arylpalladium cyanide complexes are distinct from those on reductive reductive eliminations from arylpalladium alkoxo, amido, thiolate

  我们报告了经过还原消除以形成芳腈的芳基钯氰化物配合物的分离和表征。一系列芳基钯氰化物配合物的还原消除速率表明，对芳基钯氰化物配合物的还原消除电子效应与芳基钯烷氧基、酰胺、硫醇盐和烯醇盐络合物的还原还原消除作用不同。含有芳基配体和给电子取代基的芳基钯氰化物配合物比含有芳基配体和吸电子取代基的配合物更快地还原消除芳腈。此外，芳族腈还原消除的过渡态与大多数其他芳基钯配合物发生的还原消除的过渡态大不相同。计算研究表明，芳基腈从 Pd(II) 中的还原消除是通过在结构和电子分布上与将 CO 插入钯-芳基键的过渡态更密切相关的过渡态发生的。
• Mechanistic Study of the L₂Pd-Catalyzed Reduction of Nitrobenzene with CO in Methanol: Comparative Study between Diphosphane and 1,10-Phenanthroline Complexes
  作者：Tiddo J. Mooibroek、Elisabeth Bouwman、Eite Drent

  DOI：10.1021/om200882p

  日期：2012.6.11

  and a DFT study of nitrobenzene deoxygenation intermediates to L2Pd═NPh all suggest that C7 is not the major product-releasing intermediate; all data suggest that the barrier for C7 decarbonylation (−CO) is lower than that for decarboxylation (−CO2). C7 is thus thought to be part of an “NPh reservoir” consisting of palladacycles that are mutually accessible through carbonylation/decarbonylation. Under

  在硝基苯与CO在甲醇中的反应中，已经研究了由1,10-菲咯啉（phen）或双齿二芳基二芳基膦配体L4X负载的Pd II化合物的催化活性。两种系统对乙氧基苯和偶氮苯均具有约70％的选择性，但还会产生羰基化产物（氨基甲酸苯甲酸甲酯（MPC）和N，N'-二苯基脲（DPU））和氢化产物（苯胺和DPU）。Pd II（L4X）系统还产生甲醇氧化产物（碳酸二甲酯，草酸二甲酯，水）。加入催化量的酸后，偶联反应受到抑制，有利于羰基化反应（对于Pd II（phen））或羰基化和氢化反应（对于Pd II）（L4X））。的钯环大号2 PDC（O）N（PH）OC（O）（C7）和钯-酰亚胺个体L 2 Pd═NPh（C3）被认为是可能的羰基化产物释放物种，其中L 2是苯或二膦配体L4X和L3X。phen-的配位体交换实验C7与L4X和L3X，L3X-的ESI-MS分析C7和phen- C7，和硝基苯脱氧中间体至L一个DFT研究2