(μ-Cl)2{Pd(η3-indenyl)}2 | 90624-27-4

• 英文名称: (μ-Cl)2{Pd(η3-indenyl)}2
• 英文别名: bis(μ-chloro)bis(η3-indenyl)dipalladium(II)；bis(μ-chloro)bis(η3-indenyl)palladium(II)；(μ-Cl)₂{Pd(η³-indenyl)}₂；(η3-indenyl)2(p-Cl)2Pd2；[(η3-indenyl)Pd(μ-Cl)]2
• CAS: 90624-27-4
• 化学式: C₁₈H₁₄Cl₂Pd₂
• 分子量: 514.055
• InChiKey: HKUSPEUCUPEGMF-UHFFFAOYSA-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：

  (μ-Cl)2{Pd(η3-indenyl)}2 以 二氯甲烷 、 苯 为溶剂， 生成 [(μ,η3-indenyl)(μ-Cl)Pd2(PCy3)2]*[trans-1,1'-bis(indenylidene)]
  参考文献：
  名称：

  New Palladium(II)−(η^3/5- or η¹-Indenyl) and Dipalladium(I)−(μ,η³-Indenyl) Complexes

  摘要：

  Reaction of the dimeric species [(eta(3)-Ind) Pd(A-Cl)] 2 (1) (Ind) indenyl) with NEt3 gives the complex (eta(3-5)-Ind) Pd(NEt3) Cl (3), whereas the analogous reactions with BnNH2 (Bn) PhCH2) or pyridine (py) afford the complexes trans-L2Pd(eta(1)-Ind) Cl ( L) BnNH2 ( 4), py ( 5)). Similarly, the one-pot reaction of 1 with a mixture of BnNH2 and the phosphine ligands PR3' gives the mixed-ligand, amino and phosphine species (PR3)( BnNH2) Pd(eta(1)-Ind) Cl (R = Cy (6a), Ph (6b)); the latter complexes can also be prepared by addition of BnNH2 to (A(3-5)-Ind) Pd(PR3) Cl (R) Cy (2a), Ph (2b)). Complexes 6 undergo a gradual decomposition in solution to generate the dinuclear Pd-I compounds (mu,eta(3)-Ind)(mu-Cl) Pd-2(PR3)(2) (R = Cy (7a), Ph (7b)) and the Pd-II compounds (BnNH2)(PR3) PdCl2 (R) Cy (8a), Ph (8b)), along with 1,1'-biindene. The formation of 7 is proposed to proceed by a comproportionation reaction between in situ-generated Pd-II and Pd-0 intermediates. Interestingly, the reverse of this reaction, disproportionation, also occurs spontaneously to give 2. All new compounds have been characterized by NMR spectroscopy and, in the case of 3, 4, 5, 6a, 7a, 7b, and 8a, by X-ray crystallography.

  DOI：

  10.1021/ja060747a
• 作为产物：
  描述：

  茚 、 palladium dichloride 在 sodium chloride 、 sodium carbonate 作用下， 以 甲醇 为溶剂， 反应 2.5h， 以84%的产率得到(μ-Cl)2{Pd(η3-indenyl)}2
  参考文献：
  名称：

  [EN] CROSS-COUPLING REACTION CATALYSTS, AND METHODS OF MAKING AND USING SAME
  [FR] CATALYSEURS DE RÉACTION À COUPLAGE CROISÉ, LEURS PROCÉDÉS DE PRODUCTION ET D'UTILISATION

  摘要：

  本发明提供了新型的过渡金属配体前催化剂，可用于制备活性偶联催化剂。在某些实施例中，本发明的前催化剂具有空气稳定性和耐潮湿性。本发明还提供了制备和使用本发明前催化剂的方法。

  公开号：

  WO2018183328A1

文献信息

• [EN] NOVEL PRECATALYST SCAFFOLDS FOR CROSS-COUPLING REACTIONS, AND METHODS OF MAKING AND USING SAME<br/>[FR] NOUVEAUX SUPPORTS DE PRÉ-CATALYSEURS POUR RÉACTIONS À COUPLAGE MUTUEL, ET LEURS PROCÉDÉS DE FABRICATION ET D'UTILISATION
  申请人：UNIV YALE

  公开号：WO2016057600A1

  公开（公告）日：2016-04-14

  The present invention provides novel transition-metal precatalysts that are useful in preparing active coupling catalysts. In certain embodiments, the precatalysts of the invention are air-stable and moisture-stable. The present invention further provides methods of making and using the precatalysts of the invention.

  本发明提供了新型过渡金属前催化剂，可用于制备活性偶联催化剂。在某些实施例中，本发明的前催化剂具有空气稳定性和湿度稳定性。本发明还提供了制备和使用本发明的前催化剂的方法。
• Synthesis, Electronic Structure, and Reactivity of Palladium(I) Dimers with Bridging Allyl, Cyclopentadienyl, and Indenyl Ligands
  作者：Matthew J. Chalkley、Louise M. Guard、Nilay Hazari、Peter Hofmann、Damian P. Hruszkewycz、Timothy J. Schmeier、Michael K. Takase

  DOI：10.1021/om400415c

  日期：2013.8.12

  identity of the bridging ligand. As a result of different overlap between the metal centers and the π orbitals of the bridging allyl, Cp, or indenyl ligand, Cp ligands are more likely to result in an anti relationship between the two bridging ligands, while allyl and indenyl ligands are more likely to give a syn relationship. The solid-state structures indicate that bridging allyl ligands bind the most tightly

  合成三个新的Pd（I）二聚体（μ-All）（μ-Cp）Pd（PEt 3）} 2（All = C 3 H 5，Cp = C 5 H 5），（μ-All） （μ-Ind）Pd（PEt 3）} 2（Ind = C 7 H 9）和（μ-Cp）（μ-Ind）Pd（PEt 3）} 2，其中包含桥接的烯丙基，据报道，Cp或茚基配体均由三乙基膦作为辅助配体支撑。这些新化合物的固态几何形状，电子结构和反应性已与二聚体（μ-All）2 Pd（PEt 3）} 2进行了比较。和（μ-Cp）2 Pd（PEt 3）} 2，以前已经报道过。这项工作建立了包含桥接烯丙基，Cp或茚基配体的配合物的固态和电子结构有许多相似之处。例如，在所有情况下，桥联配体通过三个碳原子与两个Pd原子键合，只有桥联基团的中心碳原子与两个金属中心键合。但是，基于桥接配体的身份也存在重要差异。由于金属中心与桥接烯丙基，Cp或茚基配体的π
• Interactions of Cationic Palladium( <scp>II</scp> )‐ and Platinum( <scp>II</scp> )‐η ³ ‐Allyl Complexes with Fluoride: Is Asymmetric Allylic Fluorination a Viable Reaction?
  作者：Lukas Hintermann、Florian Läng、Pascal Maire、Antonio Togni

  DOI：10.1002/ejic.200500795

  日期：2006.4

  The complex cations [M(η3-R2All)(PPFPz3-tBu})]+ (M = PdII, R2All = 1,3-diphenylallyl, 1,3-dicyclohexylallyl, indenyl; M = PtII, R2All = 1,3-diphenylallyl; PPFPz-3-tBu} = 3-tert-butyl-1-1-[2-diphenylphosphanyl-ferrocenyl]ethyl}-1H-pyrazole)have been prepared as salts with PF6– or SbF6–. They have been characterized by NMR spectroscopy in solution and by X-ray crystallography in the solid state. Their

  复合阳离子 [M(η3-R2All)(PPFPz3-tBu})]+ (M = PdII, R2All = 1,3-二苯基烯丙基, 1,3-二环己基烯丙基, 茚基; M = PtII, R2All = 1,3 -二苯基烯丙基；PPFPz-3-tBu} = 3-叔丁基-1-1-[2-二苯基膦酰基-二茂铁基]乙基}-1H-吡唑）已与PF6-或SbF6-形成盐。它们已通过溶液中的 NMR 光谱和固态下的 X 射线晶体学进行表征。它们与亲核和“裸”氟化物源的反应已通过多核 NMR 光谱进行了研究。PdII 复合物没有经历任何亲核取代，伴随着烯丙基氟的释放。二环己基烯丙基片段通过消除以 1,3-二烯形式释放，但与其他烯丙基配合物的非特异性分解反应占主导地位。复合物 [Pt(η3-1, 3-Ph2C3H3)(PPFPz3-tBu})]PF6 与 Me4NF 进行阴离子交换得到 [Pt(1,3-P
• New Routes to η¹- and (η³↔η⁵)-Indenylpalladium Complexes: Synthesis, Characterization, and Reactivities
  作者：Christine Sui-Seng、Gary D. Enright、Davit Zargarian

  DOI：10.1021/om034253n

  日期：2004.3.1

  The dimer ( eta(3)-Ind)Pd(mu-Cl)}(2) (6) reacts with t-BuNC to give the dimeric species (eta(1)-Ind)(t-BuNC)Pd(mu-Cl)}(2) (10), whereas reaction with PR3 gives the complexes (eta-Ind)Pd(PR3)Cl (R = Ph (4), Cy (7), Me (8), OMe (9)). Complexes 4 and (1-Me-Ind)Pd(PPh3)Cl (5) can also be prepared by reacting (PhCN)(2)PdCl2 with LiInd and PPh3. The structural characterization of complexes 4-7, 9, and 10 by H-1 and C-13 NMR spectroscopy and single-crystal X-ray diffraction studies has allowed an analysis of the indenyl ligand's mode of coordination, both in the solid-state and in solution. Compounds 4, 6, and 7 react with PhSiH3 in the absence of cocatalysts, whereas reaction with ethylene requires the presence of excess MAO to give polyethylene.
• Nakasuji, Kazuhiro; Yamaguchi, Masakazu; Murata, Ichiro, Organometallics, 1984, vol. 3, # 8, p. 1257 - 1260
  作者：Nakasuji, Kazuhiro、Yamaguchi, Masakazu、Murata, Ichiro、Tatsumi, Kazuyuki、Nakamura, Akira

  DOI：——

  日期：——