trans-(tri(p-fluorophenyl)phosphine)2PdCl2 | 916261-50-2

• 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: trans-(tri(p-fluorophenyl)phosphine)2PdCl2
• 英文别名: trans-[PdCl2(P(C6H4-4-F)3)2]；dichloropalladium;tris(4-fluorophenyl)phosphane
• CAS: 916261-50-2
• 化学式: C₃₆H₂₄Cl₂F₆P₂Pd
• 分子量: 809.85
• InChiKey: MYFPLKXRDPNWHV-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  1.73
• 重原子数：
  47
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  trans-(tri(p-fluorophenyl)phosphine)2PdCl2 、 bis(phenyl-2-thiol)phenylphosphine 在 NEt₃ 作用下， 以 二氯甲烷 为溶剂， 以83%的产率得到bis[(2-phenylthiolato)phenylphosphino-S,S',P]-tris(4-fluorophenyl)phosphine-palladium(II)
  参考文献：
  名称：

  Synthesis, characterization and catalytic evaluation in the Heck coupling reactions of S–P–S pincer complexes of the type [Pd{PhP(C6H4-2-S)2}(PAr3)]

  摘要：

  A series of palladium complexes of the type [Pd(phPS(2))(PAr3)] (phPS(2)) = [PhP(C6H4-2-S)(2)](2-) have been synthesized in good yields and their crystal structures determined. Heck coupling reactions were carried out using the [Pd(phPS(2))(PPh3)] (1), [Pd(phPS(2)){P(C6H4-4-Cl)(3)}] (2), [Pd(phPS(2)) {P(C6H4-4-F)(3)}] (3), [Pd(phPS(2)) {P(C6H4-4-CF3)(3)}] (4), [Pd(phPS(2)){P(C6H4-4-Me)(3)}] (5) and [Pd(phPS(2)) {P(C6H4-4-OMe)(3)}] (6) complexes as catalyst precursors in order to examine the potential effect of the para-substituted triarylphosphines in the reaction of bromobenzene and styrene. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2006.10.029
• 作为产物：
  描述：

  Di-<2-chlorphenyl>-phenylphosphin 以 氘代氯仿 、 二氯甲烷 为溶剂， 生成 trans-(tri(p-fluorophenyl)phosphine)2PdCl2
  参考文献：
  名称：

  Transition metal complexes containing P(C6H5)(C6H4Cl-2)2. The effect of added Lewis bases as a probe for substitution reactions occurring in ambient temperature Suzuki couplings catalyzed by Pd/P(C6H5)(C6H4Cl-2)2

  摘要：

  The reactivity of the d(8) transition metal complexes, [NiBr2(CH3OCH2CH2OCH3)] and MCl2L2 (M = Pd, Pt; L = CH3CN; L-2 = 1,5-cyclooctadiene), towards P(C6H5)(C6H4Cl-2)(2) (1) was investigated. While treatment of [PdCl2(cod)] with 2 equiv of 1 resulted in displacement of the weakly coordinating cyclooctadiene and formation of [PdCl2(P(C6H5)(C6H4Cl-2)(2))(2)], analogous reactions with [PtCl2(cod)] afforded the monosubstituted species [PtCl2(cod)(P(C6H5)(C6H4Cl-2)(2))]. The disubstituted complex [PtCl2(P(C6H5)(C6H4Cl-2)(2))(2)] was successfully obtained by treatment of [PtCl2(NCCH3)(2)] with 2 equiv of 1. However, attempts to react I with [NiBr2(CH3OCH2CH2OCH3)] were unsuccessful. The chlorinated triphenyl phosphine is quite labile and is readily displaced from [PdCl2(P(C6H5)(C6H4Cl-2)(2))(2)] by various Lewis bases including nitrogen containing ligands such as 2,2-bipyridine. The molecular structure of trans-[PdCl2(P(C6H5)(C6H4Cl-2)(2))(2)] was determined by X-ray diffraction and represents the first molecular structure determination of a transition metal complex containing 1. This complex crystallizes in the monoclinic space group P2(1)/n with a = 10.3928(3) Angstrom, b = 16.0102(4) Angstrom, c = 13.1884(4) Angstrom, beta = 90.714(2)degrees, and Z = 4. Key geometric parameters include Pd-Cl(1) = 2.309(1) Angstrom, Pd-P(1) = 2.334(1) Angstrom,- Pd-P(1)-C(7) = 118.3(2)degrees, Pd-P(1)-C(1) = 115.3(2)degrees, C(1)-C(6)-Cl(2) = 120.7(4)degrees and Cl(1)-Pd-P(1) = 85.86(4)degrees. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)01141-6
• 作为试剂：
  描述：

  苯乙烯 、 N-(5-iodoquinolin-8-yl)cyclohexanecarboxamide 在 trans-(tri(p-fluorophenyl)phosphine)2PdCl2 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 生成
  参考文献：
  名称：

  一种5-位烯基化8-酰胺基喹啉类化合物及其 一锅法制备方法

  摘要：

  本发明提供一种5‑位烯基化8‑酰胺基喹啉类化合物及其制备方法，以8‑酰胺基喹啉类化合物、卤化物、烯烃类化合物为原料，以常用的有机溶剂作反应溶剂；第一步为无金属催化，第二步常见金属催化剂作为催化剂，经历先卤化，无需分离直接与烯烃类化合物一锅法反应，经柱层析得5‑位烯基化8‑酰胺基喹啉类化合物。反应产率高、制备方法简单，成本较低，具有较好的工业应用前景。

  公开号：

  CN106938985B

文献信息

• Characterization of sites of different thermodynamic affinities on the same metal center via isothermal titration calorimetry
  作者：Eric G. Moschetta、Kristina M. Gans、Robert M. Rioux

  DOI：10.1016/j.jcat.2013.02.020

  日期：2013.6

  enthalpy, and the binding stoichiometry all in a single experiment. For systems in which two equivalents of ligand were able to bind to the Pd center, the binding sites on each Pd center in solution showed a different thermodynamic affinity for the same ligand. Changes in binding modes between different phosphorus ligands were due to steric bulk and poor electron-donating ability of such ligands. Our results

  我们研究了一系列磷配体与模型化合物PdCl 2（solv）2的结合热力学。，其中溶剂溶剂是指使用等温滴定量热（ITC）的溶剂分子。ITC允许在单个实验中定量平衡结合常数，结合焓和结合化学计量。对于其中两个当量的配体能够结合到Pd中心的系统，溶液中每个Pd中心上的结合位点对同一配体显示出不同的热力学亲和力。不同磷配体之间结合模式的变化归因于这些配体的空间体积和较弱的给电子能力。我们的结果表明，由于溶剂重组，配体结合受到强烈的焓驱动，这是本体溶剂中溶剂分子的重排以及溶剂化物种周围的溶剂分子的重排。
• Effects of PAr₃ Ligands on Direct Arylation of Heteroarenes with Isolated [Pd(2,6-Me₂C₆H₃)(μ-O₂CMe)(PAr₃)]₄ Complexes
  作者：Masayuki Wakioka、Yuki Nakamura、Yoshihiro Hihara、Fumiyuki Ozawa、Shigeyoshi Sakaki

  DOI：10.1021/om500922n

  日期：2014.11.10

  The palladium-catalyzed direct arylation of heteroarenes with aryl halides has attracted considerable attention as a simple cross-coupling process that does not need organometallic reagents. It is generally accepted that this catalysis proceeds via an arylpalladium carboxylate intermediate, which produces direct arylation products via the sequence of three elementary processes: (a) substrate coordination

  钯催化的杂芳烃与芳基卤化物的直接芳基化作为一种​​不需要有机金属试剂的简单交叉偶联方法已引起了广泛的关注。通常认为，这种催化作用是通过芳基钯羧酸盐中间体进行的，该中间体通过以下三个基本过程的序列产生直接的芳基化产物：（a）底物配位，（b）C–H键断裂和（c）C–C还原消除。本文描述了动力学调查四种PAR的效果3点使用分离的复合物上直接芳基化的配体[将Pd（2,6-ME 2 ç 6 ħ 3）（μ-O 2 CME）（PAR 3）] 4（1个：Ar ＝ Ph（a），4-MeOC 6 H 4（b），4-FC 6 H 4（c），4-F 3 CC 6 H 4（d））。虽然图1A - ð具有在固态的四聚体结构，它们是处于快速平衡与单体物种[钯（2,6--ME 2 ç 6 ħ 3）（O 2 CME-κ 2 ö）（PAR 3）]在解决方案中。配合物1a – d与2-甲基噻吩（3）和苯并噻唑（4）的THF溶液
• The 19F chemical shifts of fluorophenyl phosphine complexes of group VIII metals
  作者：W.J. Louch、D.R. Eaton

  DOI：10.1016/s0020-1693(00)89039-8

  日期：1978.1

  Abstract The 19 F chemical shifts for meta and para fluorophenyl phosphines incorportated in a range of group VIII transition metal complexes are reported. The measured shifts are used to obtain values of the o1 and σ° R parameters used to correlate the electron withdrawing and donating parameters of aromatic compounds. It is concluded that the donor or acceptor properties of a metal ion containing

  摘要据报道，在一系列VIII族过渡金属配合物中，偏氟和对氟苯基膦的19 F化学位移。测得的位移用于获得o1和σ°R参数的值，这些参数用于关联芳族化合物的吸电子和给电子参数。可以得出结论，含金属离子的部分的供体或受体性质更多地取决于存在的配体的性质，而不是取决于金属离子的形式氧化态。
• Transition metal complexes containing P(C6H5)(C6H4Cl-2)2. The effect of added Lewis bases as a probe for substitution reactions occurring in ambient temperature Suzuki couplings catalyzed by Pd/P(C6H5)(C6H4Cl-2)2
  作者：Joshua J. Stone、Robert A. Stockland、Nigam P. Rath

  DOI：10.1016/s0020-1693(02)01141-6

  日期：2003.1

  The reactivity of the d(8) transition metal complexes, [NiBr2(CH3OCH2CH2OCH3)] and MCl2L2 (M = Pd, Pt; L = CH3CN; L-2 = 1,5-cyclooctadiene), towards P(C6H5)(C6H4Cl-2)(2) (1) was investigated. While treatment of [PdCl2(cod)] with 2 equiv of 1 resulted in displacement of the weakly coordinating cyclooctadiene and formation of [PdCl2(P(C6H5)(C6H4Cl-2)(2))(2)], analogous reactions with [PtCl2(cod)] afforded the monosubstituted species [PtCl2(cod)(P(C6H5)(C6H4Cl-2)(2))]. The disubstituted complex [PtCl2(P(C6H5)(C6H4Cl-2)(2))(2)] was successfully obtained by treatment of [PtCl2(NCCH3)(2)] with 2 equiv of 1. However, attempts to react I with [NiBr2(CH3OCH2CH2OCH3)] were unsuccessful. The chlorinated triphenyl phosphine is quite labile and is readily displaced from [PdCl2(P(C6H5)(C6H4Cl-2)(2))(2)] by various Lewis bases including nitrogen containing ligands such as 2,2-bipyridine. The molecular structure of trans-[PdCl2(P(C6H5)(C6H4Cl-2)(2))(2)] was determined by X-ray diffraction and represents the first molecular structure determination of a transition metal complex containing 1. This complex crystallizes in the monoclinic space group P2(1)/n with a = 10.3928(3) Angstrom, b = 16.0102(4) Angstrom, c = 13.1884(4) Angstrom, beta = 90.714(2)degrees, and Z = 4. Key geometric parameters include Pd-Cl(1) = 2.309(1) Angstrom, Pd-P(1) = 2.334(1) Angstrom,- Pd-P(1)-C(7) = 118.3(2)degrees, Pd-P(1)-C(1) = 115.3(2)degrees, C(1)-C(6)-Cl(2) = 120.7(4)degrees and Cl(1)-Pd-P(1) = 85.86(4)degrees. (C) 2002 Elsevier Science B.V. All rights reserved.
• Synthesis, characterization and catalytic evaluation in the Heck coupling reactions of S–P–S pincer complexes of the type [Pd{PhP(C6H4-2-S)2}(PAr3)]
  作者：Valente Gómez-Benítez、Simón Hernández-Ortega、Rubén A. Toscano、David Morales-Morales

  DOI：10.1016/j.ica.2006.10.029

  日期：2007.4

  A series of palladium complexes of the type [Pd(phPS(2))(PAr3)] (phPS(2)) = [PhP(C6H4-2-S)(2)](2-) have been synthesized in good yields and their crystal structures determined. Heck coupling reactions were carried out using the [Pd(phPS(2))(PPh3)] (1), [Pd(phPS(2))P(C6H4-4-Cl)(3)}] (2), [Pd(phPS(2)) P(C6H4-4-F)(3)}] (3), [Pd(phPS(2)) P(C6H4-4-CF3)(3)}] (4), [Pd(phPS(2))P(C6H4-4-Me)(3)}] (5) and [Pd(phPS(2)) P(C6H4-4-OMe)(3)}] (6) complexes as catalyst precursors in order to examine the potential effect of the para-substituted triarylphosphines in the reaction of bromobenzene and styrene. (c) 2006 Elsevier B.V. All rights reserved.