[Pd(dppp)(CO2CF3)2] | 138488-62-7

• 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: [Pd(dppp)(CO2CF3)2]
• 英文别名: Pd(dppp)(TFA)2；[Pd(1,2-bis(diphenylphosphino)propane)(O2CCF3)2]；[Pd(1,3-bis(diphenylphosphanyl)propane)(CF3COO)2]；3-diphenylphosphanylpropyl(diphenyl)phosphane;palladium(2+);2,2,2-trifluoroacetate
• CAS: 138488-62-7
• 化学式: C₃₁H₂₆F₆O₄P₂Pd
• 分子量: 744.903
• InChiKey: GZTBZRWQGMBAJH-UHFFFAOYSA-L

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：

  [Pd(dppp)(CO2CF3)2] 、 7,11,15,28-tetracyano-1,21,23,25-tetraundecyl-2,20:3,19-dimetheno-1H,21H,23H,25H-bis[1,3]dioxocino[5,4-i:5',4'-i']benzo[1,2-d:5,4-d']-bis[1,3]benzodioxocin 以 not given 为溶剂， 以0%的产率得到[[Pd(1,3-bis(diphenylphosphino)propane)]4(7,11,15,28-tetracyano-1,21,23,25-tetraundecyl-2,20:3,19-dimetheno-1H,21H,23H,25H-bis[1,3]dioxocino[5,4-i:5',4'-i']benzo[1,2-d:5,4-d']-bis[1,3]benzodioxocin)2][CF3COO]8
  参考文献：
  名称：

  基于腔体的配位笼的自组装和阴离子包封特性

  摘要：

  已经通过自组装程序合成了两种新型的基于腔体的协调笼 7a--j 和 8a--d。控制笼自组装 (CSA) 的主要因素已确定为 (i) 螯合配体和金属前体之间的 P--M--P 角接近 90 度，(ii) Pd 和 Pt 作为金属中心， (iii) 弱配位的反离子，和 (iv) 四齿空腔配体的预组织。量热测量和动态 (1) H 和 (19) F 核磁共振实验表明 CSA 是熵驱动的。平衡笼低聚物的温度范围由空腔组分的预组织水平决定。笼子 7d 的晶体结构显示存在单个被封装的三氟甲磺酸盐阴离子。来宾竞争实验表明，笼子 7b 的封装偏好，d 遵循 BF(4)(-) > CF(3)SO(3)(-) >> PF(6)(-) 在 300 K 的顺序。 ES-MS 实验与分子建模相结合为观察到的提供了基本原理封装选择性。遵循客体溶剂化焓的基本选择性模式会因腔的大小和形状而改变，仅在 BF(4)(-) 的情况下才允许辅助溶剂分子进入。

  DOI：

  10.1021/ja0103492
• 作为产物：
  描述：

  1,3-双(二苯基膦)丙烷 以 not given 为溶剂， 生成 [Pd(dppp)(CO2CF3)2]
  参考文献：
  名称：

  基于腔体的配位笼的自组装和阴离子包封特性

  摘要：

  已经通过自组装程序合成了两种新型的基于腔体的协调笼 7a--j 和 8a--d。控制笼自组装 (CSA) 的主要因素已确定为 (i) 螯合配体和金属前体之间的 P--M--P 角接近 90 度，(ii) Pd 和 Pt 作为金属中心， (iii) 弱配位的反离子，和 (iv) 四齿空腔配体的预组织。量热测量和动态 (1) H 和 (19) F 核磁共振实验表明 CSA 是熵驱动的。平衡笼低聚物的温度范围由空腔组分的预组织水平决定。笼子 7d 的晶体结构显示存在单个被封装的三氟甲磺酸盐阴离子。来宾竞争实验表明，笼子 7b 的封装偏好，d 遵循 BF(4)(-) > CF(3)SO(3)(-) >> PF(6)(-) 在 300 K 的顺序。 ES-MS 实验与分子建模相结合为观察到的提供了基本原理封装选择性。遵循客体溶剂化焓的基本选择性模式会因腔的大小和形状而改变，仅在 BF(4)(-) 的情况下才允许辅助溶剂分子进入。

  DOI：

  10.1021/ja0103492

文献信息

• Bis(chelated) palladium(II) complexes with a diphosphine and a dinitrogen ligand: very efficient catalyst precursors in the co- and ter-polymerisation of CO and olefins
  作者：Barbara Milani、Lidia Vicentini、Anna Sommazzi、Fabio Garbassi、Elisabetta Chiarparin、Ennio Zangrando、Giovanni Mestroni

  DOI：10.1039/dt9960003139

  日期：——

  A new series of palladium(II) complexes of general formula [Pd(dppp)(L–L)][PF6]2 has been synthesised and characterised [dppp = Ph2P(CH2)3PPh2, L–L = 2,2′-bipyridine (bipy), 4,4′-dimethyl-2,2′-bipyridine, phenanthroline or 3,4,7,8-tetramethyl-1,10-phenanthroline]. The crystal structure of [Pd(dppp)(bipy)][PF6]2 has been determined. The chemical behaviour of the complexes in solution has been studied by NMR spectroscopy. Depending on the nature of the solvent, the chemical environment of palladium in solution can be either the same as in the solid state or different. Whereas in CD2Cl2 the co-ordination sphere remains intact, partial dissociation of the nitrogen ligand occurs in co-ordinating solvents. The complexes were found to be very active catalyst precursors in the CO–olefin co- and ter-polymerisation reactions. Detailed investigation of their catalytic activity allowed the catalyst precursor to be considered as the result of the assembly of different parts, each with a well defined role. In particular, the dissociated N-donor modulates the proton concentration, thus affecting the length of the polymeric chain.

  合成并表征了一系列通式为[Pd(dppp)(L-L)][PF6]2 的新钯(II)配合物[dppp = Ph2P(CH2)3PPh2、L-L = 2,2′-联吡啶（bipy）、4,4′-二甲基-2,2′-联吡啶、菲罗啉或 3,4,7,8-四甲基-1,10-菲罗啉]。[Pd(dppp)(bipy)][PF6]2 的晶体结构已经确定。核磁共振光谱研究了这些复合物在溶液中的化学特性。根据溶剂的性质，钯在溶液中的化学环境可能与固态相同，也可能不同。在 CD2Cl2 中，配位球保持完整，而在配位溶剂中，氮配体会发生部分解离。研究发现，这些配合物在一氧化碳-烯烃共聚和三聚反应中是非常活跃的催化剂前体。通过对其催化活性的详细研究，可以将催化剂前体视为由不同部分组装而成，每个部分都有明确的作用。特别是，解离的 N-供体会调节质子浓度，从而影响聚合物链的长度。
• Copolymerization of carbon monoxide with ethene catalyzed by bis-chelated palladium(II) complexes containing diphosphine and dinitrogen ligands
  作者：Claudio Bianchini、Hon Man Lee、Pierluigi Barbaro、Andrea Meli、Simonetta Moneti、Francesco Vizza

  DOI：10.1039/a903823j

  日期：——

  (napy; x=2). The structure of [Pd(meso-bdpp)(N,N′-bipy)](PF6)2·CH2Cl2 has been determined by an X-ray structural analysis. All the Pd(II) complexes have been tested as catalyst precursors for the copolymerization of carbon monoxide and ethene in methanol solution in either autoclaves or high-pressure sapphire NMR tubes. The combination of meso-bdpp and bipy at palladium, in conjuction with both 1,4-benzoquinone

  已经制备并表征了几种双螯合的钯（II）配合物，[Pd（PP）（NN）x ]（PF 6）2，它们包含二膦和二氮配体的二元组合。二膦配体包括1，3-双（二苯基膦基）丙烷（dppp），内消旋-2,4-双（二苯基膦基）戊烷（内消旋-bdpp），外消旋-2,4-双（二苯基膦基）戊烷（外消旋-bdpp）和2,2'-双（二苯基膦基乙基）戊烷（Etdppp），而二氮配体是2,2'-联吡啶（bipy; x = 1）或1,8-萘啶（napy; x = 2）。[Pd（meso -bdpp）（N，Ñ '-bipy）]（PF 6）2 ·CH 2氯2已通过X-射线结构分析来确定。在高压釜或高压蓝宝石NMR管中，所有Pd（II）配合物均已作为一氧化碳和乙烯在甲醇溶液中共聚的催化剂前体进行了测试。钯中内消旋-bdpp和联吡啶与1,4-苯醌和对甲苯磺酸的结合显示出最佳的催化性能。由立体异构体显示出[加入Pd（在不同的催化活性内消旋-bdpp）（Ñ，Ñ（PF
• Studies on palladium-bisphosphine catalyzed alternating copolymerization of CO and ethylene
  作者：He-Kuan Luo、Yuan Kou、Xi-Wen Wang、Da-Gang Li

  DOI：10.1016/s1381-1169(99)00258-7

  日期：2000.2

  Palladium(II)-bisphosphine catalyzed copolymerization of CO and ethylene was studied in detail. The results showed that DPPPr/Pd(II) mole ratio, CF3COOH/Pd(II) mole ratio and solvent greatly influence the catalytic activity. Solvent effects were studied and in detail through end group analysis. With high pressure in situ H-1-NMR technique, the signals of coordinated ethylene at 4.4 ppm and methylene linked with Pd(II) (Pd-CH2-) at 0.6 ppm were observed. With high-pressure in situ IR technique three palladium carbonyl absorptions were observed generated at 1638 cm(-1), 1616 cm(-1) and 1970 cm(-1), which may be assigned to three intermediates (3) (5) (6). With the above results, the copolymerization mechanisms were discussed. High-pressure in situ P-31-NMR experimental result showed that only mono-chelate ring complex(1) was produced when DPPPr/Pd(II) = 1; only bis-chelate ring complex (2) was produced when DPPPr/Pd(II) = 2; equimolar complex (1) and (2) were produced when DPPPr/Pd(II)=1.5. Extended X-ray absorption fine structure (EXAFS) was used to calculate the coordination number (CN) and shell radius (R, in Angstrom) of complexes (DPPPr)Pd(OCOCF3)(2) (a), (DPPBu)Pd(OCOCF3)(2) (b), (DPPEt)Pd(OCOCF3)(2) (c), (DPPPr)(2)Pd(OCOCF3)(2) (e), and two catalyst solutions or methanol freshly taken before and in the middle of copolymerization (named S1 and S2, respectively). The Pd-P bond length of complexes (a) (b) (c) are 2.25(3) Angstrom, 2.33(3) Angstrom, and 2.38(2) Angstrom, respectively, Pd-O bond length of complexes (a) (b) (c) are 2.07(3) Angstrom, 2.06(2) Angstrom and 2.05(3) Angstrom, respectively. In the order of complexes (a) (b) (c), the catalytic activity increases with Pd-P bond decreasing and Pd-O bond increasing, which may show that the chelate ring is more stable, the anions can go away more easily, and the corresponding catalyst is more efficient. The coordination number of two catalyst solutions S1 and S2 are increased by 1.9 and 0.9 compared with solid complex (a), which may show that 18-electron and five-coordinated pyramidal intermediates were produced and existed in the system besides 16-electron and four-coordinated square planar intermediates. (C) 2000 Elsevier Science B.V. All rights reserved.
• In Situ Preparation of Palladium Diphosphane Catalysts
  作者：Angelica Marson、A. Bart van Oort、Wilhelmus P. Mul

  DOI：10.1002/1099-0682(200211)2002:11<3028::aid-ejic3028>3.0.co;2-8

  日期：2002.11