[1,1'-Bis(diphenylphosphino)ferrocene]palladium(II) bromide, Pd 12.9% | 124268-93-5

• 英文名称: [1,1'-Bis(diphenylphosphino)ferrocene]palladium(II) bromide, Pd 12.9%
• 英文别名: [1,1'-bis(diphenylphosphino)ferrocene]dibromopalladium(II)；{1,1'-bis(diphenylphosphino)ferrocene} palladium dibromide；dibromo[1,1-bis(diphenylphosphino)ferrocene]palladium(II)；1,1'-bis(diphenylphosphino)ferrocene palladium dibromide；PdBr2(dppf)；[1,1‘-bis(diphenylphosphino)ferrocene]dibromopalladium(II)；[(1,1-bis(diphenylphosphino)ferrocene)Pd(Br)₂]
• CAS: 124268-93-5
• 化学式: C₃₄H₂₈Br₂FeP₂Pd
• 分子量: 820.619
• InChiKey: ARMJTLABGMKFDW-UHFFFAOYSA-L

物化性质

• 熔点：
  274-282°C

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

安全信息

• 危险性防范说明：
  P261,P264,P271,P280,P302+P352,P304+P340,P305+P351+P338,P312,P362,P403+P233,P501
• 危险性描述：
  H315,H319,H335

反应信息

• 作为反应物：
  描述：

  [1,1'-Bis(diphenylphosphino)ferrocene]palladium(II) bromide, Pd 12.9% 、 silver trifluoroacetate 以 二氯甲烷 为溶剂， 以68%的产率得到[(1,10-bis(diphenylphosphino)ferrocene)Pd(trifluoroacetate)₂]
  参考文献：
  名称：

  Isolation and structural characterization of some stable Pd(II) carboxylate complexes supported by 1,1′-bis(diphenylphosphino) ferrocene (dppf)

  摘要：

  Although catalytically active palladium phosphine carboxylates are generally unstable, a series of such complexes are stabilized by dppf, viz. Pd(O2CR)(2)(dppt) [R = CF3 I, CF2CF3 II [1,43] CF2CF2CF3 III, CHCl2 IV, o-C6H4Cl VI, CH2CO2H VII, CH=CHCO2H VIII]. They have been spectroscopically characterized and their structures determined by X-ray single-crystal crystallography. Two derivatives viz. Pd(O4C2-O,O')(dppf) IX and PdCl(O2CPh)(dppt) X are included for comparison. They are invariably mononuclear with chelating phosphine and unidentate carboxylates. The more labile (and less basic) carboxylates tend to form complexes that are more resistive to reductive decomposition. Pd(O2CPh)(2)(dppf) V decomposes readily to PdCl2(dppf) in the presence of chlorinated solvents. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(02)01645-5
• 作为产物：
  描述：

  1,1'-双(二苯基膦)二茂铁 、 以 丙酮 为溶剂， 以95%的产率得到[1,1'-Bis(diphenylphosphino)ferrocene]palladium(II) bromide, Pd 12.9%
  参考文献：
  名称：

  Synthesis, X-ray, spectroscopic and a preliminary Suzuki coupling screening studies of a complete series of dppfMX2 (M=Pt, Pd; X=Cl, Br, I)

  摘要：

  A complete series of dppfMX(2) (M = Pt, Pd; X = Cl, Br, I) compounds have been synthesized using different routes, and characterized fully. The synthesis of dppfPdI, has been achieved by reacting Pd(COD)Cl-2 with dppf in the presence of NaI. X-ray structures of dppfPdBr(2) and dppfPdI(2) have also been reported for the first time in this study. A preliminary Suzuki coupling screening study reveals that dppfPdX(2), compounds are superior to the conventional Ph3P-based catalysts and bidentate phosphine-based ligands. Reactions carried out under in situ conditions also gave a similar trend, but their respective activities were much lower than that of the fully formed catalysts. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(01)00981-0
• 作为试剂：
  描述：

  N-(6-chloropyridazin-3-yl)-1-methyl-6-oxo-1,4,5,6-tetrahydropyridazine-3-carboxamide 、 3-氯苄溴 在 1,2-二溴乙烷 、 锌 、 [1,1'-Bis(diphenylphosphino)ferrocene]palladium(II) bromide, Pd 12.9% 作用下， 以 四氢呋喃 为溶剂， 反应 17.5h， 以9%的产率得到N-(6-(3-chlorobenzyl)pyridazin-3-yl)-1-methyl-6-oxo-1,4,5,6-tetrahydropyridazine-3-carboxamide
  参考文献：
  名称：

  WO2019183587A5

  摘要：

  公开号：

  WO2019183587A5

文献信息

• Palladium-catalyzed heteroaryl thioethers synthesis overcoming palladium dithiolate resting states inertness: Practical road to sulfones and NH-sulfoximines
  作者：Johan Guilbaud、Marine Labonde、Awatef Selmi、Majed Kammoun、Hélène Cattey、Nadine Pirio、Julien Roger、Jean-Cyrille Hierso

  DOI：10.1016/j.catcom.2018.03.025

  日期：2018.6

  provide efficient synthetic access to heteroaryl sulfones in two-steps using a simple palladium–1,1′-bis[(diphenyl)phosphanyl]ferrocene catalyst to form in high yields variously functionalized heteroaromatic thioethers. Pyridinyl-containing substrates can be subsequently selectively oxidized into sulfones and NH-sulfoximines by using very mild oxidation conditions with a high functional group tolerance

  我们使用简单的钯–1,1'-双[（（二苯基）膦酰基]二茂铁催化剂，分两步提供高效率的合成途径，以高产率形成各种功能化的杂芳族硫醚。含吡啶基的底物可随后被选择性氧化为砜和氮通过使用非常温和的氧化条件和较高的官能团耐受性来制备H-亚磺酰亚胺。在钯催化的杂芳族硫醇的C–S偶联中，反应缺陷与电子缺陷性硫醇有关。我们表明，可以通过在CS耦合中成功使用2-溴杂芳烃来解决这一局限性。我们在本文中确定，在钯催化的C–S键形成中选择杂芳基亲电试剂可以克服二硫代钯盐的非循环静置惰性。这是由4-三氟甲基苯并-1-硫醇分离形成的二硫代钯盐的化学计量反应性研究，通过多核NMR和XRD对2-氯吡啶和2-溴吡啶进行表征。
• Synthesis, Characterization, and Reactivity of Palladium Fluoroenolate Complexes
  作者：Sophie I. Arlow、John F. Hartwig

  DOI：10.1021/jacs.7b09949

  日期：2017.11.15

  by palladium complexes have been reported, but palladium fluoroenolate intermediates relevant to such reactions have not been isolated or even detected previously. We report the synthesis, structural characterization, and reactivity of a series of C-bound arylpalladium fluoroenolate complexes ligated by monophosphines and bisphosphines. DPPF-ligated arylpalladium fluoroenolate complexes (DPPF = 1,1

  已经报道了由钯配合物催化的芳基与α-氟代羰基化合物的交叉偶联反应，但与这种反应相关的氟烯醇钯中间体以前没有被分离甚至检测到。我们报告了一系列由单膦和双膦连接的 C 结合芳基钯氟烯醇盐配合物的合成、结构表征和反应性。源自单氟酯、二氟酯、二氟酰胺和二氟乙腈的 DPPF 配位芳基氟烯醇化钯复合物 (DPPF = 1,1-双(二苯基膦)-二茂铁) 以高产率进行还原消除。与含有更多吸电子氟烯醇基团和较短 Pd-C(enolate) 键的配合物相比，含有较少吸电子氟烯醇基团和较长 Pd-C(enolate) 键的配合物的还原消除速度更快。这些 C 结合的氟烯醇化物配合物的还原消除速率明显快于类似的三氟甲基配合物的还原消除速率。
• Palladium(II) phosphine thiocarboxylates. Structures of cis-Pd(κS-SOCMe)2(dppf) [dppf=1,1′-bis(diphenylphosphino)ferrocene] and trans-Pd(κS-SOCMe)2(PPh3)2
  作者：Yew Chin Neo、Jagadese J Vittal、T.S.Andy Hor

  DOI：10.1016/s0022-328x(01)00916-0

  日期：2001.12

  Although palladium phosphine acetates are generally unstable and served as catalytic precursors, their monothioacetate analogues can be isolated and structurally characterized. Spectroscopic and X-ray single-crystal crystallographic analyses suggested that Pd(κS-SO}CMe)2(P2) [P2=dppf, I; P=PPh3, II] are mononuclear with thioacetate coordinates in a unidentate manner through sulfur. Dppf imposes a

  尽管乙酸钯膦膦酸酯通常是不稳定的并且用作催化前体，但是它们的单硫代乙酸酯类似物可以被分离并在结构上表征。光谱和X射线单晶结晶分析表明，加入Pd（κ小号-S ö} CME）2（P 2）[P 2 = DPPF，我; P = PPh 3，II ]是单核的，具有硫代乙酸盐配位体，并通过硫以不明方式存在。DPPF对I施加顺式构型，而PPh 3促进II的反式结构。这些化合物以异构纯的形式获得-没有证据表明硫代乙酸盐螯合或桥联或二膦桥联。在我组的硫代乙是显著更屏蔽在II比我由相邻膦的pH值环。
• Mapping the reaction pathway in palladium-catalyzed cross-coupling reactions
  作者：John M. Brown、Neil A. Cooley

  DOI：10.1021/om00116a010

  日期：1990.2