[Pd(μ-Cl)(C6F5)(tetrahydrothiophene)]2 | 70634-64-9

• 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(μ-Cl)(C6F5)(tetrahydrothiophene)]2
• 英文别名: [Pd2(μ-Cl)2(C6F5)2(tht)2]；Chloropalladium(1+);1,2,3,4,5-pentafluorobenzene-6-ide;thiolane
• CAS: 70634-64-9；75715-63-8
• 化学式: C₂₀H₁₆Cl₂F₁₀Pd₂S₂
• 分子量: 794.209
• InChiKey: MOBUOCVXXKEDML-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  8.77
• 重原子数：
  36
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  [Pd(μ-Cl)(C6F5)(tetrahydrothiophene)]2 在 KI 作用下， 以 二氯甲烷 、 丙酮 、 苯 为溶剂， 生成 IPd(μ-bis(diphenylphosphino)methane)2Pd(C6F5)
  参考文献：
  名称：

  中性和阳离子五氟苯基钯（I）衍生物的合成。双核钯（I）配合物中异氰化物的插入与配位

  摘要：

  PdX（C 6 F 5）（dpm）2（dpm =双（二苯基膦基）甲烷; X = Cl，Br，I，CNO或C 6 F 5）与Pd 2（dba）3 CHCl 3（dba =二苄叉基丙酮）之间的反应）给出五氟苯基钯（I）衍生物[XPd（μ-dpm）2 Pd（C 6 F 5）]。用过量的配体L处理[ClPd（μ-dpm）2 Pd（C 6 F 5）]，并在NaBPh 4存在下得到阳离子络合物[LPd（μ-dpm）2 Pd（C 6 F 5）5）] BPh4（L ＝ PPh 3，P（OPh）3，吡啶或四氢噻吩（tht））。与异氰酸酯反应RNC生成三种不同类型的化合物：（a）异氰酸酯基团插入PdPd键[（μ-RNC）{; XPd（μ-dpm）2 Pd（C 6 F 5）}的产物;]（X ＝ C 6 F 5； R ＝对甲苯基； X ＝ Cl，R ＝对甲苯基或Cy）。（b）带有末端异氰酸酯的阳离子络合物[（RNC）Pd（μ-dpm）2

  DOI：

  10.1016/s0022-328x(00)99212-x

文献信息

• Cyano-organopalladate complexes and their cyanobridged derivatives
  作者：R. Usón、J. Forniés、P. Espinet、A. Arribas

  DOI：10.1016/s0022-328x(00)84528-3

  日期：1980.10

  The preparations of anionic complexes of the types Q2[(C6F5)xPd(CN)4−x] (x = 1, 2(cis and trans), 3; Q = ammonium or phosphonium cation) and (N-n-Bu4)[(η3-C3H5)Pd(CN)2] are described. Their reactions with palladium perchlorato complexes give polynuclear neutral, anionic or cationic cyanobridged derivatives. The proposed structures of the new complexes are based on their IR spectra.

  Q 2 [（C 6 F 5）x Pd（CN）4- x ]（x = 1，2（顺式和反式），3; Q =铵或phospho阳离子）和（Nn -Bu 4）[（η 3 -C 3 H ^ 5）的Pd（CN）2 ]中描述。他们与高氯酸钯配合物的反应产生了多核的中性，阴离子或阳离子氰基桥联衍生物。新络合物的拟议结构基于其红外光谱。
• Mechanism of the Stille Reaction. 2. Couplings of Aryl Triflates with Vinyltributyltin. Observation of Intermediates. A More Comprehensive Scheme
  作者：Arturo L. Casado、Pablo Espinet、Ana M. Gallego

  DOI：10.1021/ja001511o

  日期：2000.12.1

  The mechanism of the [PdL4]-catalyzed couplings between R-OTf (R = pentahalophenyl; L = PPh3, AsPh3) and Sn(CH=CH2)Bu-3 has been studied. The addition of LiCl favors the coupling for L = AsPh3 in THF but retards it for L = PPh3. Separate experiments show that for L = AsPhs, LiCl accelerates the otherwise very slow and rate-determining oxidative addition of the aryl triflate to [PdL4], leading to trans[PdRClL2]. Therefore, the overall process is accelerated. For L = PPh3, the rate-determining step is the transmetalation. Complex trans-[PdRXL2],with X = Cl, is formed in the presence of LiCl, whereas an equilibrium mixture mainly involving species with X = TfO, L, or S (S = solvent) is established in the absence of LiCl. Since the transmetalation is slower for X = Cl than for the other complexes, the overall process is retarded by addition of LiCl. The transmetalation in complexes trans-[PdRXL2], with X = Cl, follows the S(E)2(cyclic) mechanism proposed in Part 1 (Casado, A. L.; Espinet, P. J. Am. Chem. Sec. 1998, 120, 8978-8985), giving the coupling product R-CH=CH2 directly. For X = TfO or, L rather stable intermediates trans[PdR(CH=CH2)L-2] are detected, Supporting an SE2(open) mechanism. The I;ey:intermediates undergoing transmetalation in the conditions arid solvents most commonly used in the literature have been identified.;The operation of S(E)2(cyclic) and S(E)2(open) pathways emphasizes common aspects of the Stille reaction with the Hiyama reaction where, using (RSiF3)-Si-2 that is chiral at the alpha -carbon of R retention or inversion gt the transmetalated chiral carbon can be-induced. This helps us to understand the contradictory stereochemical outcomes in the literature for Stille couplings using (RSnR3)-Sn-2 derivatives that are chiral Bt the a-carbon of R-2 and suggests that stereocontrol of the Stille reaction might be achieved.
• P(CH₂CH₂Py)<i>_n</i>Ph₃_-<i>_n</i> (Py = 2-Pyridyl; <i>n</i> = 1, 2, 3) as Chelating and as Binucleating Ligands for Palladium
  作者：Juan A. Casares、Pablo Espinet、Katerina Soulantica、Isabel Pascual、A. Guy Orpen

  DOI：10.1021/ic970745e

  日期：1997.11.1

  Several neutral palladium(II) complexes of the type [PdRCl(PNn)] with the ligands P(CH2CH2Py)Ph-2 (PN), P(CH2CH2Py)(2)Ph (PN2), and P(CH2CH2Py)(3) (PN3) have been prepared by reacting the corresponding phosphines with [Pd-2(mu-Cl)(2)R-2(tht)(2)] (R = C6Cl2F3, C6F5; tht = tetrahydrothiophene). In all these complexes, the ligands act as bidentate P,N-chelating ligands. Abstraction of the chloride with AgBF4 leads to the formation of the dimeric compounds [Pd2R2(PN2)(2)](BF4)(2) and [Pd2R2(PN3)(2)](BF4)(2), in which the PNn ligands act as P,N-chelating and P,N-bridging ligands. The bridges are labile, and exchange experiments on mixtures of the complexes with different R groups show the equilibrium in solution between the dimeric ''pure'' complexes and the mixed complexes [Pd-2(C6F5)(C6Cl2F3)(PNn)(2)](2+). The structure of the complex [Pd-2(C6Cl2F3)(2)(P(CH2CH2Py)(2)Ph)(2)](BF4)(2) has been studied by X-ray diffraction.
• Bidenizimidazolate as bridging ligand in bi-, tri- and tetranuclear gold(I) or gold(I) and palladium(II) complexes
  作者：R. Usón、J. Gimeno、J. Forniés、F. Martínez、C. Fernandez

  DOI：10.1016/s0020-1693(00)95396-9

  日期：1981.1