Pd(CN(2,6-(2,6-(i-Pr)2C6H3)2C6H3))2 | 1182649-23-5

• 英文名称: Pd(CN(2,6-(2,6-(i-Pr)2C6H3)2C6H3))2
• 英文别名: Pd(CN(2,6-(2,6-(i-Pr)₂C₆H₃)₂C₆H₃))₂；Pd(CN-2,6-(2,6-(i-Pr)₂C₆H₃)₂C₆H₃)₂；Pd[2,6-(2,6-(i-Pr)2C6H3)2)phenylisocyanide]；Pd(CN-2,6-(2,6-iPr2C6H3)2C6H3)2
• CAS: 1182649-23-5
• 化学式: C₆₂H₇₄N₂Pd
• 分子量: 953.703
• InChiKey: BOMCENTUENJGGD-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：

  Pd(CN(2,6-(2,6-(i-Pr)2C6H3)2C6H3))2 在 亚硝基苯 作用下， 以 苯 为溶剂， 反应 24.0h， 以34%的产率得到1,3-Bis[2,6-di(propan-2-yl)phenyl]-2-isocyanatobenzene
  参考文献：
  名称：

  氧化还原非纯亚硝基芳烃配体的溶液动力学：映射持久性金属配位的一氧化氮自由基形成的电子标准

  摘要：

  已经基于固态表征技术建立了金属配位的C-有机亚硝基芳烃的氧化还原非纯，但是这类金属配位的自由基的溶液相性质却相对不足。在该报告中，双-亚硝基苯的溶液相性能和动态双基复合反式-Pd（κ 1 - ñ -PhNO）2（CNAR Dipp2）2给出。这种复杂的，这是最好的描述为包含单独降低phenylnitroxide自由基配体，示出了经历容易的亚硝基苯离解在溶液中，以形成metalloxaziridine的Pd（η 2 - Ñ，O -PhNO）（CNAr Dipp2）2，因此不是溶液中的持久性物种。之间的平衡反式-Pd（κ 1 - ñ -PhNO）2（CNAR Dipp2）2，加入Pd（η 2 - Ñ，ö -PhNO）（CNAR Dipp2）2，和自由亚硝基苯被建立在溶液中，与感metalloxaziridine主要受到青睐。努力通过加入过量的亚硝基苯的扰乱这种平衡表明，形成反式-Pd（κ 1 -

  DOI：

  10.1021/acs.inorgchem.5b01252
• 作为产物：
  描述：

  [TlPd(CN(2,6-(2,6-(i-Pr)₂C₆H₃)₂C₆H₃))₂](3,5-(CF₃)₂C₆H₃) 以 四氢呋喃 为溶剂， 生成 Pd(CN(2,6-(2,6-(i-Pr)2C6H3)2C6H3))2
  参考文献：
  名称：

  Metal-only Lewis pairs between group 10 metals and Tl(i) or Ag(i): insights into the electronic consequences of Z-type ligand binding

  摘要：

  金属-金属路易斯酸碱对之间的金属和Tl(i)以及Ag(i)之间的金属-金属路易斯酸碱对，使我们能够深入了解路易斯酸配位的电子影响。

  DOI：

  10.1039/c5sc03104d
• 作为试剂：
  描述：

  对溴甲苯 、 2-联苯硼酸 在 Pd(CN(2,6-(2,6-(i-Pr)2C6H3)2C6H3))2 、 sodium t-butanolate 作用下， 以 异丙醇 为溶剂， 反应 8.0h， 以73%的产率得到4-methyl-o-terphenyl
  参考文献：
  名称：

  Synthetic and Mechanistic Interrogation of Pd/Isocyanide-Catalyzed Cross-Coupling: π-Acidic Ligands Enable Self-Aggregating Monoligated Pd(0) Intermediates

  摘要：

  Despite the large number of judiciously designed ligands that have been exploited in palladium-catalyzed cross-coupling protocols, the incorporation of ligands bearing appreciable pi-acidic properties has remained significantly underexplored. Herein, we demonstrate that well-defined and low-coordinate Pd-0 complexes supported by m-terphenyl isocyanides function as competent catalysts for the Suzuki Miyaura cross-coupling of aryl bromides and arylboronic acids. Two-coordinate Pd(CNArDiPP2)(2) was active for the coupling of unhindered aryl bromides at room temperature in 2-propanol, while increasing the temperature to 60 degrees C allowed for the use of mono-or di-ortho-substituted aryl bromides. Oxidative addition of the aryl bromide was shown to proceed via a dissociative mechanism, implicating monoligated Pd(CNArDipp2) as the catalytically active intermediate. Attempts to access this fleeting species via activation of the Pd-II monoisocyanide PdCl(eta(3)-C3H5)(CNArDipp2) with alkoxide base yielded the dinuclear Pd-I species mu-C3H5(mu-O'Pr)[Pd(CNArDipp2)](2). Although dinuclear Pd-I complexes are often produced as off-cycle species when using complexes of the type PdCl(eta(3)-allyl)L as precatalysts, this represents the first time that the comproportionation product (mu-allyl)(mu-Cl)[PdL](2) has been observed to undergo nucleophilic substitution with alkoxide, despite the fact that activating conditions for these precatalysts typically employ alkoxide bases. Remarkably, this alkoxide complex can undergo, beta-hydride elimination with expulsion of acetone and propene to produce two equivalents of, catalytically active Pd(CNArDipp2), which can self-aggregate to yield the isolable tripalladium cluster Pd-3(eta(2)-Dipp-mu-CNArDipp2)(3). This cluster is catalytically competent for the Suzuki Miyaura reaction and functions as a formal source of monoligated Pd(CNArDipp2) in solution.

  DOI：

  10.1021/acs.organomet.7b00035

文献信息

• Direct Observation of β-Chloride Elimination from an Isolable β-Chloroalkyl Complex of Square-Planar Nickel
  作者：Alex E. Carpenter、Andrew J. McNeece、Brandon R. Barnett、Alexander L. Estrada、Charles C. Mokhtarzadeh、Curtis E. Moore、Arnold L. Rheingold、Charles L. Perrin、Joshua S. Figueroa

  DOI：10.1021/ja508956q

  日期：2014.11.5

  characterization, and decomposition kinetics of the four-coordinate pentachloroethyl nickel complex, NiCl(CCl2CCl3)(CNAr(Mes2))2 (Ar(Mes2) = 2,6-(2,4,6-Me3C6H2)2C6H3). This complex is a unique example of a kinetically persistent β-chloroalkyl in a system relevant to coordination-insertion polymerization of polar olefins. Kinetic analysis of NiCl(CCl2CCl3)(CNAr(Mes2))2 decomposition indicates that β-chloride

  这里报告的是四配位五氯乙基镍配合物 NiCl(CCl2CCl3)(CNAr(Mes2))2 (Ar(Mes2) = 2,6-(2,4,6-Me3C6H2) 的分离、结构表征和分解动力学)2C6H3)。该复合物是与极性烯烃的配位插入聚合相关的系统中动力学持久性 β-氯代烷基的独特例子。NiCl(CCl2CCl3)(CNAr(Mes2))2 分解的动力学分析表明，β-氯化物 (β-Cl) 消除是通过单分子机制进行的，不需要 CNAr(Mes2) 配体的初始解离。结果表明，直接的 β-Cl 消除途径可用于四配位的 10 族金属氯乙烯聚合系统。
• Bond Activation, Substrate Addition and Catalysis by an Isolable Two-Coordinate Pd(0) Bis-Isocyanide Monomer
  作者：Liezel A. Labios、Matthew D. Millard、Arnold L. Rheingold、Joshua S. Figueroa

  DOI：10.1021/ja905338x

  日期：2009.8.19

  active for oxidative addition reactions and readily reacts with benzyl chloride and mesityl bromide to form Pd(Cl)(Bz)(CNAr(Dipp2))(2) and Pd(Br)(Mes)(CNAr(Dipp2))(2), respectively. Room-temperature Suzuki-Miyaura cross-coupling reactions are mediated by Pd(CNAr(Dipp2))(2). Coordinatively and electronically unsaturated substrates also react with Pd(CNAr(Dipp2))(2). Addition of thallium(I) triflate (TlOTf)

  二价前体 PdCl(2)(CNAr(Dipp2))(2)（Dipp = 2,6-二异丙基苯基）的镁金属还原提供了可分离的双配位 Pd(0) 双异氰化物 Pd(CNAr(Dipp2) )(2)，这是第一个稳定的零价钯单体异氰化物配合物。在添加 CNAr(Dipp2) 的情况下，对 Pd(CNAr(Dipp2))(2) 的变温 (1)H NMR 和 FTIR 研究表明，游离的和配位的异氰化物会发生快速交换，但组分不会形成稳定的三异氰化物络合物。双异氰化物 Pd(CNAr(Dipp2))(2) 对氧化加成反应很活跃，很容易与苄基氯和甲基溴反应形成 Pd(Cl)(Bz)(CNAr(Dipp2))(2) 和 Pd(Br )(Mes)(CNAr(Dipp2))(2)。室温 Suzuki-Miyaura 交叉偶联反应由 Pd(CNAr(Dipp2))(2) 介导。配位和电子不饱和底物也会与 Pd(CNAr(Dipp2))(2)
• Redox Noninnocence of Nitrosoarene Ligands in Transition Metal Complexes
  作者：Neil C. Tomson、Liezel A. Labios、Thomas Weyhermüller、Joshua S. Figueroa、Karl Wieghardt

  DOI：10.1021/ic2005979

  日期：2011.6.20

  radical anion. In addition to the electron transfer series, the synthesis and characterization of the Fe complex [Fe(TIM)(NCCH3)(PhNO)][(PF6)2] (TIM = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene) allows for comparison of the geometric and spectroscopic features associated with metal-to-ligand π-backbonding as opposed to (PhNO)•1– formation. Throughout these series of complexes

  关于亚硝基芳烃（ArNO）配体与后过渡金属配位的研究用于提供与PhNO电子传递系列相关的几何，光谱和计算参数的第一个定义。实验上，Pd络合物PdCl 2（PhNO）2，PdL 2（PhNO）2和PdL 2（TolNO）（L = CNAr Dipp2 ; Ar Dipp2 = 2,6-（2,6- i Pr 2 C 6 H 3）2 -C 6 H 3）的特征是含有（PhNO）0，（PhNO）•1–和（TolNO）2–配体，以及与该电子转移序列相关的结构和光谱变化，为这些和相关的含ArNO的后期过渡金属配合物的广泛计算研究提供了基础。最显着的从结果是PDL的基态电子结构的明确的表征2（PHNO）2，发现含有η第一可分离，过渡金属离子络合物1 - ñ结合的π-nitrosoarene自由基阴离子。除电子转移系列外，Fe络合物[Fe（TIM）（NCCH 3）（PhNO）] [（PF 6）2的合成和表征]（TIM