(1,5-cyclooctadiene)bis(3,5-dichloro-2,4,6-trifluorobenzene)palladium(II) | 198142-61-9

• 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: (1,5-cyclooctadiene)bis(3,5-dichloro-2,4,6-trifluorobenzene)palladium(II)
• 英文别名: (COD)Pd(C₆F₃Cl₂)₂；Pd(dctbf)₂(cod)；Pd(3,5-dichloro-2,4,6-trifluorobenzene)₂(cod)；cis-[Pd(C6F3Cl2)2(1,5-cyclooctadiene)]；cis-[Pd(1,5-cyclooctadiene)(3,5-dichlorotrifluorophenyl)2]；Pd(3,5-dichlorotrifluorophenyl)2(1,5-cyclooctadiene)；(1Z,5Z)-cycloocta-1,5-diene;2,4-dichloro-1,3,5-trifluorobenzene-6-ide;palladium(2+)
• CAS: 198142-61-9
• 化学式: C₂₀H₁₂Cl₄F₆Pd
• 分子量: 614.538
• InChiKey: GOOJROXTWZJYQO-PHFPKPIQSA-N

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：

  (1,5-cyclooctadiene)bis(3,5-dichloro-2,4,6-trifluorobenzene)palladium(II) 、 以 氘代四氢呋喃 为溶剂， 生成 (CH2(C8H17O)(C6H2)(C13H7N4)(Pd(3,5-C6Cl2F3)2))4*4H2O
  参考文献：
  名称：

  A deep tetranuclear metallo-cavitand with bis(aryl) palladium bridges

  摘要：

  一种基于顺式双-全卤代芳基Pd(II)的中性金属空穴受体，在深杯[4]芳烃的角上配位。通过1H和19F NMR实验研究了金属空穴受体及其与其他杯[4]芳烃的包合物。

  DOI：

  10.1039/c0cc00534g
• 作为产物：
  描述：

  dichloro(cycloocta-1,5-diene)palladium (II) 、 1,3,5-三氯-2,4,6-三氟苯 在 n-BuLi 作用下， 以 乙醚 、 正己烷 为溶剂， 以95%的产率得到(1,5-cyclooctadiene)bis(3,5-dichloro-2,4,6-trifluorobenzene)palladium(II)
  参考文献：
  名称：

  3,5-二氯三氟苯基配合物，具有简​​单19 F NMR结构探针的芳基衍生物。Pd和Pt配合物的一般前体的合成1

  摘要：

  高产率合成顺式-[MR 2（COD）]（M = Pd，Pt; R = 3,5-C 6 Cl 2 F 3），顺式-[MR 2（THF）2 ]（M = Pd; Pt），反式-[PdR 2 L 2 ]（L = tht; SMe 2），反式-[PtR 2（SMe 2）2 ]和[M 2（μ- Cl）2 R 2 L 2 ]（ M = Pd，L = NCPh，tht，SMe 2; 报告M = Pt，L = tht）。这些络合物是用于制备几乎以定量产率包含顺式-MR 2，反式-MR 2和MC1R部分的其他络合物的一般前体。因此，通过用其他配体置换COD，THF，tht或SMe 2，可以制备具有一个或两个芳基环的任何配合物的几乎任何异构体。与其他多氟苯基相比，这些配合物的19 F NMR光谱简单，并给出了这种部分氟化的配体的光谱优势的一些实例。

  DOI：

  10.1016/s0022-328x(97)00424-5

文献信息

• Enthalpy of ligand substitution in cis organopalladium complexes with monodentate ligands
  作者：Gorka Salas、Juan A. Casares、Pablo Espinet

  DOI：10.1039/b910055e

  日期：——

  The enthalpy for the substitution reaction cis-[PdRf2(THF)2] + 2 L →cis-[PdRf2L2] + 2THF (THF = tetrahydrofuran) has been measured in THF by calorimetric methods for Rf = 3,5-dichloro-2,4,6-trifluorophenyl, L = PPh3, AsPh3, SbPh3, PMePh2, PCyPh2, PMe3, AsMePh2, or L2 = dppe (1,2-bis(diphenylphosphino)ethane), dppf (1,1′-bis(diphenylphosphino)ferrocene). The values determined show that the substitution enthalpy has a strong dependence on the electronic and steric properties of the ligand. The study of the consecutive substitution reactions cis-[PdRf2(THF)2] + L →cis-[PdRf2L(THF)] + THF, and cis-[PdRf2L(THF)] + L →cis-[PdRf2L2] + THF has been carried our for L = PPh3 and L = PCyPh2. The first substitution is clearly more favorable for the bulkier leaving ligand, but the second gives practically the same ΔH value for both cases, indicating that the differences in steric hindrance happen to compensate the electronic differences for both ligands. The X-ray structures of cis-[PdRf2(PMePh2)2], cis-[PdRf2(dppe)] and cis-[PdRf2(dppf)] are reported.

  通过量热方法在THF中测量了取代反应cis-[PdRf2(THF)2] + 2 L →cis-[PdRf2L2] + 2THF（THF = 四氢呋喃）的焓变，其中Rf = 3,5-二氯-2,4,6-三氟苯基，L = PPh3、AsPh3、SbPh3、PMePh2、PCyPh2、PMe3、AsMePh2或L2 = dppe（1,2-双(二苯膦)乙烷）、dppf（1,1'-双(二苯膦)二茂铁）。测定值表明，取代焓强烈依赖于配体的电子和立体性质。对连续取代反应cis-[PdRf2(THF)2] + L →cis-[PdRf2L(THF)] + THF和cis-[PdRf2L(THF)] + L →cis-[PdRf2L2] + THF的研究进行了L = PPh3和L = PCyPh2的情况。第一次取代显然对较大的离去配体更有利，但第二次取代实际上在两种情况下给出了相同的ΔH值，表明立体阻碍的差异恰好补偿了两种配体的电子差异。报道了cis-[PdRf2(PMePh2)2]、cis-[PdRf2(dppe)]和cis-[PdRf2(dppf)]的X射线结构。
• Neutral versus polycationic coordination cages: a comparison regarding neutral guest inclusion
  作者：György Szalóki、Vincent Croué、Magali Allain、Sébastien Goeb、Marc Sallé

  DOI：10.1039/c6cc04610j

  日期：——

  A neutral self-assembled container synthesized from a concave -extended tetrathiafulvalene (exTTF) ligand and the cis-Pd(dctfb)2(cod) complex (dctfb = 3,5-dichloro-2,4,6-trifluorobenzene; cod = 1,5-cyclooctadiene) is described. This molecular host exhibits a good...

  一个中性的自组装容器，由凹形-延伸的四硫富瓦烯（exTTF）配体和顺式-Pd（dctfb）2（cod）配合物（dctfb = 3,5-dichloro-2,4,6-三氟苯; cod =描述了1，5-环辛二烯。该分子宿主表现出良好的...
• Self-Assembled Squares and Triangles by Simultaneous Hydrogen Bonding and Metal Coordination
  作者：Laura J. Marshall、Javier de Mendoza

  DOI：10.1021/ol400326r

  日期：2013.4.5

  Through the combination of hydrogen bonding and metal-templated self-assembly, molecular squares and molecular triangles are observed in chloroform solution upon the complexation of hydrogen-bonded dimers of para-pyridyl-substituted 2-ureido-4-[1H]-pyrlmidinone (UPy) and an appropriate cis-substituted palladium complex. Molecular modeling studies and NMR analysis confirmed the presence of two distinct structures In solution: the tubular structure of the molecular square and propeller-bowl structure of the molecular triangle.
• Structural and dynamic studies in solution of anionic dinuclear azolato-bridged palladium(II) complexes
  作者：Raquel de la Cruz、Pablo Espinet、Ana M Gallego、Jose M Martı́n-Alvarez、Jesús M Martı́nez-Ilarduya

  DOI：10.1016/s0022-328x(02)01772-2

  日期：2002.12

  Detailed analysis of the F-19-NMR spectra of the boat-shaped complexes (NBu4)(2)[Pd-2(mu-LL)(2)R-4] (R = 3,5-C6Cl2F3) (LL = pyrazolate (pz), 1; dimethylpyrazolate (dmpz), 2), HH- (head-to-head) and HT- (head-to-tail) (NBu4)(2)[Pd-2(mu-LL)(2)R-4] (LL = 3-methylpyrazolate (mpz), 3; indazolate (indz), 4), (NBu4)(2)[Pd-2(mu-dmpz)(mu-LL)R-4] (LL = mpz, 6; indz, 7), and (NBu4)(2)[R2Pd(mu-LL)(2)Pd(C6F5)(2)] (LL = pz, 8; dmpz, 9) affords valuable structural information in solution. The substituents of the azolate ligands, which reduce the dihedral angle between the coordination planes of the two metals, place the endo F-ortho of different PdR2 fragments at short distances. A single-crystal X-ray structure has been obtained for compound HT-4 and the distances between F-ortho compared with that calculated from the NMR spectra. The study of the dynamic processes for these complexes reveals the involvement of different mechanisms such as: (a) rotation of the R groups, (b) boat-boat inversion of the six-membered Pd(mu-LL)(2)Pd ring, (c) sigma-1,2-metallotropic shift, and (d) associative exchange of PdR2 fragments between 1 and mononuclear complexes. (C) 2002 Elsevier Science B.V. All rights reserved.
• An Aryl Exchange Reaction with Full Retention of Configuration of the Complexes:  Mechanism of the Aryl Exchange between [PdR₂L₂] Complexes in Chloroform (R = Pentahalophenyl, L = Thioether)
  作者：Arturo L. Casado、Juan A. Casares、Pablo Espinet

  DOI：10.1021/om970721f

  日期：1997.12.1

  The complexes [Pd(3,5-C6Cl2F3)(2)L-2] and [Pd(C6F5)(2)L-2] (L = SC4H8 (tht), or SMe2) react in CCl3D to give a mixture also containing the heteroaryl products [Pd(3,5-C6Cl2F3)(C6F5)L-2], whereas for L = PPh3, AsPh3, 2-picoline, 4-picoline, or 1/2COD, this exchange is not observed. The F-19 NMR kinetic study supports that the scrambling of the aryl groups takes place with retention of configuration at both Pd centers via a triply-bridged binuclear activated complex [L(C6Cl2F3)Pd(mu-C6Cl2F3)(mu-C6F5)(mu-L)Pd(C6F5)L].(double dagger) The aryl double bridge is supported by a bridging S-donor ligand facilitating an otherwise difficult exchange (not observed for other weak L ligands, such as picolines, lacking a second lone pair). This constitutes the first reported example of reversible migration of sigma-C-bonded groups between bis-organo Pd(II) complexes proceeding without cis-trans isomerization. The isomerization process is also observed, occurring at a much slower rate.