(PdCl(N,N-dimethylformamide))2(μ-azobenzene(-2H)) | 864439-66-7

• 英文名称: (PdCl(N,N-dimethylformamide))2(μ-azobenzene(-2H))
• 英文别名: PdCl(N,N-dimethylformamide)(μ-azobenzene)PdCl(N,N-dimethylformamide)
• CAS: 864439-66-7；864439-72-5；864515-21-9
• 化学式: C₁₈H₂₂Cl₂N₄O₂Pd₂
• 分子量: 610.144
• InChiKey: QKFYAZRWKNTNKK-SSXBCGQJSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  1,1'-双(二苯基膦)二茂铁 、 (PdCl(N,N-dimethylformamide))2(μ-azobenzene(-2H)) 以 丙酮 为溶剂， 反应 72.0h， 以98.8%的产率得到
  参考文献：
  名称：

  老化和球磨作为合成Pd（II）光敏剂的低能耗和环境友好方法

  摘要：

  简单而有效的固态合成方法，老化和球磨（液体辅助研磨，LAG），已被用于实现与dicyclopalladated偶氮苯三苯基膦（TPP）和1,1'-双（二苯基膦基）二茂铁（DPPF）的反应（DMF）的PdCl（μ-R 1 C ^ 6 ħ 3 N═NC 6 ħ 3 - [R 2）的PdCl（DMF）中，R 1 = H，OCH 3，N（CH 3）2和R 2 = H，NO 2。衰老过程首次应用于Pd（II）杂配物的形成。两个合成步骤导致四种类型的四-或五配位络合物（TPP）的PdCl {（μ-Cl）的（μ-R的1 ç 6 ħ 3 N═NC 6 ħ 3 - [R 2）}的Pd（TPP）1A - 3A， （TPP）2的PdCl（μ-R 1 C ^ 6 ħ 3 N═NC 6 ħ 3 - [R 2）的PdCl（TPP）2 1B - 3B，{的PdCl（μ-Cl）的（μ-R 1 C ^ 6 ħ 3N═NC 6

  DOI：

  10.1021/om500008v
• 作为产物：
  描述：

  双(乙腈)氯化钯(II) 、 N,N-二甲基甲酰胺 、 偶氮苯 以 N,N-二甲基甲酰胺 为溶剂， 生成 (PdCl(N,N-dimethylformamide))2(μ-azobenzene(-2H))
  参考文献：
  名称：

  Simple Route to the Doubly ortho-Palladated Azobenzenes:  Building Blocks for Organometallic Polymers and Metallomesogens

  摘要：

  A new class of doubly cyclopalladated complexes, {PdCl(dmf)}(2-)(mu-azb) (1) and {PdCl(dmf)}(2)(mu-aazb) (2), has been prepared in dimethylformamide (dmf) by reaction of azobenzene (azb) and 4-aminoazobenzene (aazb), respectively, with an excess of PdCl2(CH3CN)(2) complex. Recrystallization of 1 and 2 in dimethyl sulfoxide (dmso) yields complexes {PdCl(dmso)}(2)(mu-azb) (3) and {PdCl(dmso)}(2)(mu-aazb) (4), respectively. The crystal structures of 1 and 4 have been determined by X-ray diffraction. All complexes are characterized by H-1 and C-13 NMR spectra and elemental analysis. In both crystal structures, solvent molecules are bound to palladium through oxygen atoms and oriented trans to carbon. In view of greater preference of palladium to nitrogen and sulfur atoms, the experimental structures were rationalized by quantum-chemical calculations and confirmed as the most stable isomers.

  DOI：

  10.1021/ic050747w

文献信息

• Synthesis and Characterization of Dicyclopalladated Complexes of Azobenzene Derivatives by Experimental and Computational Methods
  作者：Darko Babić、Manda Ćurić、Krešimir Molčanov、Gregor Ilc、Janez Plavec

  DOI：10.1021/ic8010234

  日期：2008.11.17

  aromatic ring having the strong electron-withdrawing substituent at the para position. In all cases, the metalated carbon and N,N-dimethylformamide or dimethylsulfoxide ligands are mutually trans, whereas the pyridine ligands are in the cis arrangement. cis/trans isomerism in the isolated compounds is explained by comparing the calculated energies of isomeric structures. All of the complexes absorb strongly

  一系列偶氮苯及其不对称取代衍生物的双环钯配合物，其中LPdCl（mu-AZB）LPdCl}，其中AZB为偶氮苯，4-甲基偶氮苯，4-氨基偶氮苯或4-（二甲基氨基）-4'-硝基偶氮苯L是N，N-二甲基甲酰胺，二甲基亚砜或吡啶。通过X射线衍射分析以及（1）1 H NMR，IR，UV-vis和荧光分析确定了它们的结构和光谱性质。通过量子化学计算合理化了实验结果。已经解决了几种配合物的晶体结构，并且首次证明环钯可发生在对位具有强吸电子取代基的偶氮苯芳环上。在所有情况下，金属碳和氮 N-二甲基甲酰胺或二甲基亚砜配体是相互反式的，而吡啶配体是顺式的。通过比较计算出的异构体结构能，可以解释分离出的化合物中的顺/反异构现象。所有的配合物在可见光区域都具有很强的吸收能力，根据随时间变化的密度泛函理论计算，大部分吸收可归因于配体内pi-> pi *或金属到配体的电荷转移跃迁。观察到与4-氨基偶氮苯或4-（二
• New insight into solid-state molecular dynamics: mechanochemical synthesis of azobenzene/triphenylphosphine palladacycles
  作者：Dominik Cinčić、Marina Juribašić、Darko Babić、Krešimir Molčanov、Primož Šket、Janez Plavec、Manda Ćurić

  DOI：10.1039/c1cc15377c

  日期：——

  Solid-state reactions of dicyclopalladated azobenzenes and triphenylphosphine lead to the thermodynamically favorable bridged complexes. It was demonstrated for the first time that very complex molecular dynamics involving a series of structural transformations is also feasible in the solid state.

  二环palpalated偶氮苯和三苯基膦的固态反应导致热力学上有利的桥连配合物。首次证明，涉及一系列结构转变的非常复杂的分子动力学在固态中也是可行的。
• Reversible Gas–Solid Ammonia N–H Bond Activation Mediated by an Organopalladium Complex
  作者：Marina Juribašić Kulcsár、Ivan Halasz、Ana Budimir、Krunoslav Užarević、Stipe Lukin、Andrea Monas、Franziska Emmerling、Janez Plavec、Manda Ćurić

  DOI：10.1021/acs.inorgchem.7b00422

  日期：2017.5

  N–H bond activation of gaseous ammonia is achieved at room temperature in a reversible solvent-free reaction using a solid dicyclopalladated azobenzene complex. Monitoring of the gas–solid reaction in real-time by in situ solid-state Raman spectroscopy enabled a detailed insight into the stepwise activation pathway proceeding to the final amido complex via a stable diammine intermediate. Gas–solid

  在室温下，使用固体二环钯配合的偶氮苯络合物，可逆的无溶剂反应可实现气态氨的N–H键活化。通过原位固态拉曼光谱实时监测气固反应，可以深入了解逐步的活化途径，即通过稳定的二胺中间体进入最终的酰胺基络合物。允许隔离和中间和最终产物酰胺，其中介绍了第一dipalladated复杂与钯的后续结构表征气固合成II（μ-NH - 2）-Pd II桥。气固反应很容易通过与钯的偶氮苯骨架构象转换有关的颜色变化进行。该反应以类似的方式在溶液中进行，并通过UV-vis和NMR光谱进行表征，显示出逐步形成酰胺基络合物的途径。将实验数据与密度泛函理论计算相结合，我们提出了由外源氨辅助的这种杂合NH键活化的逐步机理。
• Dicyclopalladated Complexes of Asymmetrically Substituted Azobenzenes: Synthesis, Kinetics and Mechanisms
  作者：Marina Juribašić、Ana Budimir、Snježana Kazazić、Manda Ćurić

  DOI：10.1021/ic402017v

  日期：2013.11.4

  Two series of new dicyclopalladated complexes (DMF)PdCl(mu-(RC6H3N)-C-1=NC6H3R2)PdCl(DMF)} of 4,4'-functionalized azobenzenes with substituents of varying electron-donating or electron-withdrawing strength (R-1 = H, NMe2; R-2 = H, Cl, Br, I, OMe, PhNH, CO2H, SO3Na, or NO2) have been synthesized and fully characterized. H-1 NMR spectroscopy along with the ESI mass spectrometry unambiguously identified the new complexes in the solution, and their solid-state structures were determined by X-ray crystallography. The presence of easily exchangeable solvent ligands was confirmed by H-1 NMR spectroscopy, X-ray experiments, and ESI mass spectrometry. The complexes were additionally characterized by UV-vis and fluorescence spectroscopies. The effect of different 4,4'-substituents on the formation rate of mono- and dicyclopalladated azobenzenes was studied by UV-vis spectroscopy. The experimental results are complemented by the quantum-chemical (DFT) calculations in order to rationalize the kinetic results as well as substituent effects on the reaction rates. It was found that the mono- and dicyclopalladation reactions of azobenzenes proceed in two consecutive processes, adduct formation and palladation steps. The rate-determining step in both palladations is the breaking of the ortho C-H bond, which has been confirmed as an electrophilic substitution process by Hammett correlations and DFT calculations.