bis(benzonitrile)palladium(II) chloride

• 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: bis(benzonitrile)palladium(II) chloride
• 英文别名: PdCl₂(PhCN)₂；Benzonitrile;palladium(2+);chloride
• 化学式: 2C₇H₅N*2Cl*Pd
• 分子量: 383.573
• InChiKey: WIPONBSEQHWANB-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.44
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bis(benzonitrile)palladium(II) chloride 、 (乙基硫代)丙酮 以 二氯甲烷 为溶剂， 以70%的产率得到((R)-ethyl(2-oxopropyl)-l4-sulfaneyl)(ethyl(2-oxopropyl)-l4-sulfaneyl)palladium(IV) chloride
  参考文献：
  名称：

  Mono- and polynuclear chloro complexes of palladium(II) with α-substituted thioethers

  摘要：

  Palladium dichloro bis-benzonitrile reacts with alpha-substituted thioethers to give the square-planar complexes [PdCl2(RSCH(2)Z)(2)] (1-6) (1-4: R = Me, Z = C(O)OMe (1), C(O)OEt (2), C(O)Omenthyl(-) (3), C(O)Me (4); (5): R = Et, Z = C(O)Me; (6). R - Me, Z = CH(OMe)(2)). Complex 1 crystallizes in the space group P2(1)/a, with Z = 2 in an elementary cell whose dimensions are a = 9.116(1), b = 8.659(1), c = 10.351(2) Angstrom and beta = 112.2(1)degrees. Its structure (SHELXL-93, R-1 0.021 and R-2w 0.0597) shows a marked deviation from the ideal square geometry to reduce the steric repulsion between the ester group of the sulfur ligand and the chlorine atom in cis position. The one-pot reaction of the chloro complexes 2 or 3 with silver acetate affords the corresponding trimers [Pd-3(mu-OAc)(3)(mu-RSCHZ)(3)] (7, 8), previously obtained by reacting palladium acetate with MeSCH(2)Z. Complex 7 undergoes, with KCI or HCl, an OAc- -Cl- exchange reaction to give the two chloro-bridged isomers [PdCl(MeSCHC(O)OEt)](n) (9, 10: n = 2, 4). The Cl-bridge in dimer 9 is broken by triphenylphosphine to give the monomeric complex [Pd-Cl(MeSCHC(O)OEt)(PPh3)]. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(99)00527-7
• 作为试剂：
  描述：

  1,1'-(1,2-乙炔二基)二(4-氟苯) 、 4,4-difluoro-8-(4-methylphenyl)-4-bora-3a,4a-diaza-s-indacene 在 bis(benzonitrile)palladium(II) chloride 、 特戊酸银 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 12.0h， 以81%的产率得到
  参考文献：
  名称：

  Pd-Catalyzed Direct C–H Functionalization/Annulation of BODIPYs with Alkynes to Access Unsymmetrical Benzo[b]-Fused BODIPYs: Discovery of Lysosome-Targeted Turn-On Fluorescent Probes

  摘要：

  A highly efficient palladium-catalyzed direct C-H functionalization/annulation of BODIPYs with alkynes has been developed for the first time to construct a series of unsymmetrical benzo[b]-fused BODIPYs from readily available starting materials. These unsymmetrical benzo[b]-fused BODIPYs exhibit remarkably red-shifted emissions and larger Stokes shifts than classical BODIPY dyes. Cell imaging experiments and cytotoxicity assays demonstrate that BODIPYs 4c and 4d have specific lysosome-labeling capacities, turn-on fluorescence emissions in cells, and low cytotoxicity.

  DOI：

  10.1021/acs.joc.8b01239

文献信息

• Catalytic activities in direct arylation of novel palladium<i>N</i>-heterocyclic carbene complexes
  作者：Senem Akkoç、Yetkin Gök

  DOI：10.1002/aoc.3220

  日期：2014.12

  Eight novel palladium N‐heterocyclic carbene (Pd‐NHC) complexes were synthesized by the reaction of chloro 1,3‐dialkylbenzimidazolin‐2‐ylidene silver(I) complexes with bis(benzonitrile)palladium(II) chloride in dichloromethane. These eight Pd‐NHC complexes are as follows: bis[1‐phenyl‐3‐(2,4,6‐trimethylbenzyl)benzimidazol‐2‐ylidene]dichloropalladium(II), bis[1‐phenyl‐3‐(2,3,5,6‐tetramethylbenzyl)b

  八种新型钯N杂环卡宾（Pd-NHC）络合物是通过氯1,3-二烷基苯并咪唑啉-2-亚银（I）络合物与双（苄腈）氯化钯（II）在二氯甲烷中的反应合成的。这八个Pd-NHC配合物如下：双[1-苯基-3-（2,4,6-三甲基苄基）苯并咪唑-2-亚烷基]二氯钯（II），双[1-苯基-3-（2,3 ，[5,6-四甲基苄基]苯并咪唑-2-亚丙基]二氯钯（II），双[1-苯基-3- [2,3,4,5,6-五甲基苄基]苯并咪唑-2-亚丙基]二氯钯（II），双[1-苯基-3-（3,4,5-三甲氧基苄基）苯并咪唑-2-亚丙基]二氯钯（II），双[1-（2-二乙基氨基乙基）-3-（3-甲基苄基）苯并咪唑-2-亚苄基]二氯钯（II），双[1-（2-二乙基氨基乙基）-3-（2,3,5,6-四甲基苄基）苯并咪唑-2-亚丙基]二氯钯（II），双[1-（2-吗啉代乙基）-3-萘甲基甲基苯并咪唑-2-亚炔基]二氯钯（II）和
• Reactions involving transition metals
  作者：Brian L. Booth、Sylvia Casey、Robert P. Critchley、Robert N. Haszeldine

  DOI：10.1016/s0022-328x(00)83412-9

  日期：1982.3

  afford air-stable adducts. 2,3-Dichloro-1,4,5,6,7,7-hexafluorobicyclo[2.2.1]hepta-2,5-diene (3) gives only [PtCl2(PPh3)2] with [Pt(Ph3P)4], but a low yield of an adduct was obtained with [Pd(PPh3)4]. The diene 1 also reacts with Fe(CO)5 to form the complex [(C7H2F6)Fe(CO)4], and with [Rh(C2H4)2(acac)] to give [(C7H2F6)Rh(acac)] in which the diene acts as a bidentate ligand. Similar products could not

  1,2,3,4,7,7-六氟双环[2.2.1]庚二烯（1）和2,3-双（三甲基锡）-1,4,5,6,7,7-六氟双环[2.2.1]庚2,5-二烯（2）与[M（Ph 3 P）4 ]（M = Pt，Pd）反应，制得空气稳定的加合物。2,3-二氯-1,4,5,6,7,7-六氟双环[2.2.1]庚-2,5-二烯（3）仅产生[PtCl 2（PPh 3）2 ]和[Pt（Ph 3 P）4 ]，但是用[Pd（PPh 3）4 ]得到低的加合物收率。二烯1也与Fe（CO）5反应形成配合物[（C 7 H 2F 6）Fe（CO）4，并与[Rh（C 2 H 4）2（acac）]一起生成[（C 7 H 2 F 6）Rh（acac）]，其中二烯充当双齿配体。无法从2和3的反应中分离出相似的产物。从2和[Rh（CO）之间的反应中已分离出一种稳定的加合物，据信是[C 7 F 6（SnMe 3）2 } Rh（CO）2（μ-Cl）2
• New palladium-<i>bis</i>(oxazoline)-phosphine complexes: synthesis, characterization and catalytic application in alkoxycarbonylation of alkynes
  作者：Mansur B. Ibrahim、Rami Suleiman、Bassam El Ali

  DOI：10.1080/00958972.2016.1163688

  日期：2016.4.17

  catalyst systems have been optimized by screening the type of palladium complexes and also by varying the reaction parameters including the reaction time, solvent, and temperature. A mechanism of the catalytic cycle based on a N-protonated palladium bis(oxazoline) phosphine active species was proposed for the alkoxycarbonylation reaction.

  摘要 合成了新的阳离子钯-双(恶唑啉)-膦 (Pd-BOX-PR3) 配合物（Pd-BOX-B 和 Pd-BOX-C），并使用 1H、13C 和 31P NMR、FTIR 光谱和电喷雾进行了表征。电离质谱 (ESI-MS)。新的配合物被用作炔烃与各种醇作为亲核试剂的烷氧基羰基化的催化剂。羰基化以高区域选择性和优异的产率产生了 gem-α,β-不饱和酯异构体 (3)。通过筛选钯配合物的类型以及改变反应参数（包括反应时间、溶剂和温度）来优化催化剂体系。提出了一种基于 N-质子化钯双 (恶唑啉) 膦活性物质的催化循环机制，用于烷氧基羰基化反应。
• A BODIPY-functionalized Pd^II photoredox catalyst for Sonogashira C–C cross-coupling reactions
  作者：Komadhie C. Dissanayake、Peters O. Ebukuyo、Yasser J. Dhahir、Kraig Wheeler、Hongshan He

  DOI：10.1039/c9cc01365b

  日期：——

  We report for the first time a BODIPY-functionalized dichloro(1,10-phenanthroline)palladium(ii) complex as an efficient photoredox catalyst for the Sonogashira C–C cross-coupling between phenylacetylene derivatives and iodobenzene derivatives with yields up to 92% under visible light illumination at room temperature.

  我们首次报道了一种BODIPY功能化的二氯(1,10-邻菲啰啉)钯(II)配合物，作为一种高效的光氧化还原催化剂，可在室温下可见光照射下，促使苯基乙炔衍生物与碘苯衍生物之间的Sonogashira C-C交叉偶联反应，产率高达92%。
• Cyclopalladation in the Periphery of a NHC Ligand as the Crucial Step in the Synthesis of Highly Active Suzuki-Miyaura Cross-Coupling Catalysts
  作者：Agnes Fizia、Maximilian Gaffga、Johannes Lang、Yu Sun、Gereon Niedner-Schatteburg、Werner R. Thiel

  DOI：10.1002/chem.201702877

  日期：2017.10.17

  reactivities of all these compounds were investigated in detail as well as their performance in the catalytic Suzuki–Miyaura cross‐coupling reaction. It turned out that the C,C‐coordinated derivatives exhibit high catalytic activities in the coupling of arylboronic acids with aryl chlorides, which is consistent with the generally accepted mechanistic ideas on substrate activation.

  从2,4-二氯嘧啶开始，可通过五步反应序列获得4-（2-二烷基氨基）嘧啶基官能化的间苯二甲酰氯。已经找到了导致这些配体衍生的钯NHC配合物的两种途径：通过与相应的NHC-AgCl配合物进行重金属化，可以获得C，N配位的钯（II）配合物。在吡啶中和在K 2 CO 3存在下用咪唑鎓盐处理二氯化钯生成环金属化的化合物，从而得到C，C配位的化合物。详细研究了所有这些化合物的反应性及其在Suzuki-Miyaura催化交叉偶联反应中的性能。结果表明，C，C配位的衍生物在芳基硼酸与芳基氯的偶联中表现出高催化活性，这与普遍接受的底物活化机理相一致。