Pd(Ph2P(CH2)3PPh2)(tosylate)2 | 128321-28-8

• 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(Ph2P(CH2)3PPh2)(tosylate)2
• 英文别名: Pd(1,3-bis(diphenylphosphino)propane)(OTs)₂；Pd(dppp)(OTs)₂；bis(p-toluenesulfonyloxy)(1,3-bis(diphenylphosphine)propane)palladium(II)；(1,3-bis(diphenylphosphino)pronane)Pd(p-toluenesulfonic acid(-H))2；[Pd(1,2-bis(diphenylphosphino)propane)(OSO2C6H4CH3)2]；(dppp)Pd(TsO)2；3-diphenylphosphanylpropyl(diphenyl)phosphane;4-methylbenzenesulfonate;palladium(2+)
• CAS: 128321-28-8
• 化学式: C₄₁H₄₀O₆P₂PdS₂
• 分子量: 861.265
• InChiKey: QFFFXUMHQBAHTL-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.97
• 重原子数：
  52.0
• 可旋转键数：
  10.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  86.74
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  Pd(Ph2P(CH2)3PPh2)(tosylate)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][OSO2C6H4CH3]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(Ph2P(CH2)3PPh2)(tosylate)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

• Ethylene and carbon monoxide copolymerization catalyzed by supported palladium catalyst
  作者：Olga M. Chukanova、Kirill A. Alpherov、Gennadiy P. Belov

  DOI：10.1016/j.molcata.2010.03.033

  日期：2010.6.15

  The kinetics of the copolymerization of ethylene with carbon monoxide catalyzed by (dppp)Pd(TsO)2 (I) has been investigated under homogeneous conditions and in slurry with supported catalyst I/P (P: polymer support polyketone (PK)), at different catalyst concentrations. The specific rate reduced to gram of Pd of the initial stage of reaction is going up with increasing catalyst concentration, and the

  （dppp）Pd（TsO）2（I）催化的乙烯与一氧化碳的共聚动力学已在均相条件下和在负载有催化剂I / P（P：聚合物载体聚酮（PK））的淤浆中进行了研究。不同的催化剂浓度。随着催化剂浓度的增加，反应初始阶段降低到克Pd的比值正在增加，而第二大动力学阶段的比值则随着催化剂负载量的增加而降低。
• 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.
• Drent, Eite, Pure and Applied Chemistry, 1990, vol. 62, p. 661 - 670
  作者：Drent, Eite

  DOI：——

  日期：——