(Pd(OCOCF₃)₂(1,2-bis(diphenylphosphino)ethane)) | 168129-77-9

• 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(OCOCF₃)₂(1,2-bis(diphenylphosphino)ethane))
• 英文别名: (Pd(OCOCF₃)₂(dppe))；[Pd(1,2-bis(diphenylphosphino)ethane)(trifluoroacetato)2]；[Pd(1,2-bis(diphenylphosphanyl)ethane)(CF3COO)2]；[Pd(dppe)(TFA)2]；2-Diphenylphosphanylethyl(diphenyl)phosphane;palladium(2+);2,2,2-trifluoroacetate
• CAS: 168129-77-9
• 化学式: C₃₀H₂₄F₆O₄P₂Pd
• 分子量: 730.876
• InChiKey: WSOZLLLUMHOUHM-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.85
• 重原子数：
  43
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  (Pd(OCOCF₃)₂(1,2-bis(diphenylphosphino)ethane)) 、 三苯基膦 、 2-氰基苯硼酸 以 氘代甲醇 为溶剂， 反应 24.0h， 生成 [Pd{C₆H₄(CH₂CN)-2}(1,2-bis(diphenylphosphino)ethane)(PPh₃)](OCOCF₃)
  参考文献：
  名称：

  钯（II）催化的炔烃与2-（氰甲基）苯基硼酸酯的环化反应生成3,4-二取代的2-萘胺

  摘要：

  1,2-双（二苯基膦基）乙烷（dppe）连接的钯（II）配合物催化内部炔烃与2-（氰基甲基）苯基硼酸酯的环化反应，从而以良好的收率提供3,4-二取代的-2-萘胺。环化反应在温和和中性条件下进行，需要甲醇作为必要溶剂。除对称炔烃外，被芳基，烷基和炔基取代的不对称炔烃也参与环化反应，得到相应的带有吸电子sp 2的2-萘胺。-和sp-carbons优先位于C-3位置。在硼酸酯中包括在氰基甲基部分上的烷基或烷氧基和在苯环上的卤素原子的取代基与反应条件相容。通过用硼酸酯和炔烃插入钯（II）配合物进行金属转移，然后将生成的烯基钯（II）亲核加成到分子内氰基中来进行环化。化学计量反应表明，甲醇溶剂对于重金属化和催化剂再生均有效。

  DOI：

  10.1021/acs.joc.5b02378
• 作为产物：
  描述：

  palladium diacetate 、 三氟乙酸 、 1,2-双(二苯基膦)乙烷 以 乙醚 为溶剂， 以78.7%的产率得到(Pd(OCOCF₃)₂(1,2-bis(diphenylphosphino)ethane))
  参考文献：
  名称：

  Studies on palladium-bisphosphine catalyzed alternating copolymerization of CO and ethylene

  摘要：

  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.

  DOI：

  10.1016/s1381-1169(99)00258-7
• 作为试剂：
  描述：

  (5-溴-2-碘苯基)甲醇 在 氯化亚砜 、 (Pd(OCOCF₃)₂(1,2-bis(diphenylphosphino)ethane)) 、 palladium diacetate 、 三乙胺 、 2-(二环己基膦基)联苯 作用下， 以 1,4-二氧六环 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.5h， 生成 7-bromo-3,4-diphenylnaphthalen-2-amine
  参考文献：
  名称：

  钯（II）催化的炔烃与2-（氰甲基）苯基硼酸酯的环化反应生成3,4-二取代的2-萘胺

  摘要：

  1,2-双（二苯基膦基）乙烷（dppe）连接的钯（II）配合物催化内部炔烃与2-（氰基甲基）苯基硼酸酯的环化反应，从而以良好的收率提供3,4-二取代的-2-萘胺。环化反应在温和和中性条件下进行，需要甲醇作为必要溶剂。除对称炔烃外，被芳基，烷基和炔基取代的不对称炔烃也参与环化反应，得到相应的带有吸电子sp 2的2-萘胺。-和sp-carbons优先位于C-3位置。在硼酸酯中包括在氰基甲基部分上的烷基或烷氧基和在苯环上的卤素原子的取代基与反应条件相容。通过用硼酸酯和炔烃插入钯（II）配合物进行金属转移，然后将生成的烯基钯（II）亲核加成到分子内氰基中来进行环化。化学计量反应表明，甲醇溶剂对于重金属化和催化剂再生均有效。

  DOI：

  10.1021/acs.joc.5b02378

文献信息

• Large Kinetic Isotope Effects for the Protonolysis of Metal–Methyl Complexes Are Not Reliable Mechanistic Indicators
  作者：Valerie J. Scott、Jay A. Labinger、John E. Bercaw

  DOI：10.1021/om200432b

  日期：2011.8.22

  several palladium and platinum methyl complexes (with release of methane) had suggested the possibility that observation of an unusually large kinetic isotope effect, consistent with significant contributions from quantum mechanical tunneling, might be diagnostic of a mechanism involving direct protonation of the metal–methyl bond, as opposed to one proceeding via a metal hydride intermediate. By extension

  早期对几种钯和铂甲基配合物（释放甲烷）进行质子水解的研究表明，观察到异常大的动力学同位素效应（与量子机械隧穿的重大贡献相一致）可能是诊断涉及直接质子化的机理的可能性。金属-甲基键，与通过金属氢化物中间体进行的操作相反。通过将这些度量扩展到更广泛的复合体，我们发现不支持所提出的相关性。
• 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
• Palladium(II)-Catalyzed Annulation of Alkynes with 2-(Cyanomethyl)phenylboronates Leading to 3,4-Disubstituted 2-Naphthalenamines
  作者：Hirokazu Tsukamoto、Taishi Ikeda、Takayuki Doi

  DOI：10.1021/acs.joc.5b02378

  日期：2016.3.4

  palladium(II) complexes catalyze the annulation of internal alkynes with 2-(cyanomethyl)phenylboronates to provide 3,4-disubstituted-2-naphthalenamines in good yields. The annulation reaction proceeds under mild and neutral conditions and requires methanol as an essential solvent. In addition to symmetrical alkynes, unsymmetrical alkynes substituted by aryl, alkyl, and alkynyl groups participate in

  1,2-双（二苯基膦基）乙烷（dppe）连接的钯（II）配合物催化内部炔烃与2-（氰基甲基）苯基硼酸酯的环化反应，从而以良好的收率提供3,4-二取代的-2-萘胺。环化反应在温和和中性条件下进行，需要甲醇作为必要溶剂。除对称炔烃外，被芳基，烷基和炔基取代的不对称炔烃也参与环化反应，得到相应的带有吸电子sp 2的2-萘胺。-和sp-carbons优先位于C-3位置。在硼酸酯中包括在氰基甲基部分上的烷基或烷氧基和在苯环上的卤素原子的取代基与反应条件相容。通过用硼酸酯和炔烃插入钯（II）配合物进行金属转移，然后将生成的烯基钯（II）亲核加成到分子内氰基中来进行环化。化学计量反应表明，甲醇溶剂对于重金属化和催化剂再生均有效。
• 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.