cis-dichloro-2-(phenylazo)pyridine palladium(II) | 155515-51-8

• 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: cis-dichloro-2-(phenylazo)pyridine palladium(II)
• 英文别名: Pd(phenylazopyridine)(chloride)2；[PdCl2(2-phenylazopyridine)]；[PdCl2(phenylazapyridine)]；[PdCl2(pap)]；Pd(pap)Cl2
• CAS: 155515-51-8
• 化学式: C₁₁H₉Cl₂N₃Pd
• 分子量: 360.539
• InChiKey: FSLWIDPVBFSBJT-VPOCKCTCSA-L

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：

  cis-dichloro-2-(phenylazo)pyridine palladium(II) 在 NaOH 、 O₂ 作用下， 以 水 、 乙腈 为溶剂， 以70%的产率得到
  参考文献：
  名称：

  Facile regiospecific aromatic hydroxylation in palladium azopyridines and structural characterization of phenolato product

  摘要：

  The reaction of Na2PdCl4 with 2-(arylazo)pyridines (A) in ethanol affords yellow complexes of composition [PdACl2] in which the PdCl2 fragment has a cis configuration [nu(Pd-Cl): 350, 365 cm-1]. Upon treating [PdACl2] with dilute sodium hydroxide in air the pendent aryl group is selectively hydroxylated at the ortho position, affording the phenolato complex [PdBCl] in high yields [B- is deprotonated 2-(2'-hydroxyarylazo)pyridine]. A possible reaction pathway is proposed by analogy with the hydroxylation of certain organic compounds by OH-/O2. The crystal and molecular structure of one [PdBCl] complex is reported. In the highly planar complex, the Pd-N(azo) length is significantly shorter than the Pd-N(pyridine) length. A single Pd-Cl stretch at 365 cm-1 characterizes [PdBCl] which, unlike [PdACl2], has a structured intense absorption in the visible region near 670 nm.

  DOI：

  10.1016/s0277-5387(00)83022-3
• 作为产物：
  描述：

  sodium tetrachloropalladate(II) 、 苯基(吡啶-2-基)二氮烯 以 乙醇 为溶剂， 以90%的产率得到cis-dichloro-2-(phenylazo)pyridine palladium(II)
  参考文献：
  名称：

  Facile regiospecific aromatic hydroxylation in palladium azopyridines and structural characterization of phenolato product

  摘要：

  The reaction of Na2PdCl4 with 2-(arylazo)pyridines (A) in ethanol affords yellow complexes of composition [PdACl2] in which the PdCl2 fragment has a cis configuration [nu(Pd-Cl): 350, 365 cm-1]. Upon treating [PdACl2] with dilute sodium hydroxide in air the pendent aryl group is selectively hydroxylated at the ortho position, affording the phenolato complex [PdBCl] in high yields [B- is deprotonated 2-(2'-hydroxyarylazo)pyridine]. A possible reaction pathway is proposed by analogy with the hydroxylation of certain organic compounds by OH-/O2. The crystal and molecular structure of one [PdBCl] complex is reported. In the highly planar complex, the Pd-N(azo) length is significantly shorter than the Pd-N(pyridine) length. A single Pd-Cl stretch at 365 cm-1 characterizes [PdBCl] which, unlike [PdACl2], has a structured intense absorption in the visible region near 670 nm.

  DOI：

  10.1016/s0277-5387(00)83022-3

文献信息

• Regioselective <i>ortho</i> Amination of Coordinated 2-(Arylazo)pyridine. Isolation of Monoradical Palladium Complexes of a New Series of Azo-Aromatic Pincer Ligands
  作者：Debabrata Sengupta、Nabanita Saha Chowdhury、Subhas Samanta、Pradip Ghosh、Saikat Kumar Seth、Serhiy Demeshko、Franc Meyer、Sreebrata Goswami

  DOI：10.1021/acs.inorgchem.5b02110

  日期：2015.12.7

  In an unusual reaction of [Pd(L1)Cl2] (L1 = 2-(arylazo)pyridine) with amines, a new series of palladium complexes [Pd(L2•–)Cl] (L2 = 2-((2-amino)arylazo)pyridine) (1a–1h) were isolated. The complexes were formed via N–H and N–C bond cleavage reactions of 1°/2° and 3° amines, respectively, followed by regioselective aromatic ortho-C–N bond formation reaction and are associated with ortho-C–H/ortho-C–Cl

  在[Pd（L 1）Cl 2 ]（L 1 = 2-（芳基偶氮）吡啶）与胺的不寻常反应中，一系列新的钯配合物[Pd（L 2•–）Cl]（L 2 = 2- （（2-氨基）芳基偶氮）吡啶）（1a – 1h）被分离出来。将复合物通过1°/ 2°和3°胺，分别，随后区域选择性芳香N-H和N-C键的断裂反应形成的邻-C-N键形成反应，并且与相关联的邻- C-H /邻位C–Cl键激活。发现包括芳族和脂族在内的多种胺可有效地生产空气稳定的络合物。通过它们的X射线结构确定来证实所得复合物的身份。还努力了解该反应的机理。进行了一系列实验，这些实验指向初始配体还原，然后是配体内电子转移。检查这些配合物的结构参数（1）表明原位生成的配体与Pd II配位中心是这些空气稳定的单自由基配合物的骨干。通过各种光谱技术，包括循环伏安法，可变温度磁化率测量，电子顺磁共振和紫外可见光谱，进一步研究了分离出的复合物的分子和电子结构
• Isomeric separation in donor–acceptor systems of Pd(ii) and Pt(ii) and a combined structural, electrochemical and spectroelectrochemical study
  作者：Naina Deibel、David Schweinfurth、Jan Fiedler、Stanislav Záliš、Biprajit Sarkar

  DOI：10.1039/c1dt10856e

  日期：——

  Compounds of the form [(pap)M(Q2−)] (pap = phenylazopyridine; Q = 3,5-di-tert-butyl-benzoquinone, M = Pd, 1a and 1b, M = Pt, 2a and 2b; Q = 4-tert-butyl-benzoquinone, M = Pd, 3a and 3b; M = Pt, 4a and 4b) were synthesized in a one-pot reaction. The geometrical isomers, which are possible because of the built in asymmetry of these ligands, have been separated by using different temperatures and variable solubility. Structural characterization of 1b shows that the metal centers are in a square planar environment, the pap ligand is in the unreduced neutral state and the quinones are in the doubly reduced, Q2−catecholate form. Cyclic voltammetric measurements on the complexes display two one-electron oxidations and two one-electron reductions. EPR and vis-NIR spectra of the one-electron oxidized forms of the complexes indicate that the first oxidation takes place on the Q2− ligands to produce a metal bound semiquinone (Q˙−) radical. Reduction takes place on the pap ligand, generating metal bound pap˙− as seen from the 14N (I = 1) coupling in their EPR spectrum. All the complexes in their [(pap)M(Q2−)] neutral forms show strong absorptions in the NIR region which are largely LLCT (ligand to ligand charge transfer) in origin. These NIR bands can be tuned over a wide energy range by varying the metal center as well as the Q ligand. In addition, the intensity of NIR bands can be switched on and off by a simple electron transfer at relatively low potentials. DFT studies were used to corroborate these findings.

  通过单锅反应合成了[(pap)M(Q2â)]形式的化合物（pap = 苯并吡啶；Q = 3,5-二叔丁基苯醌，M = Pd，1a 和 1b；M = Pt，2a 和 2b；Q = 4-叔丁基苯醌，M = Pd，3a 和 3b；M = Pt，4a 和 4b）。由于这些配体具有内在的不对称，因此可以通过不同的温度和不同的溶解度来分离几何异构体。1b 的结构特征显示，金属中心处于方形平面环境中，pap 配体处于未还原的中性状态，而醌则处于双重还原的 Q2âcatecholate 形式。对这些配合物进行的循环伏安测量显示了两个单电子氧化和两个单电子还原。复合物的单电子氧化型的 EPR 和 vis-NIR 光谱表明，Q2â 配体发生了第一次氧化，生成了与金属结合的半醌（QËâ）自由基。从它们的 EPR 光谱中的 14N (I = 1) 偶联可以看出，还原发生在 pap 配体上，生成与金属结合的 papËâ。所有[(pap)M(Q2â)]中性形式的配合物在近红外区域都显示出很强的吸收，这主要源于配体间电荷转移（LLCT）。通过改变金属中心和 Q 配体，可以在很宽的能量范围内调整这些近红外波段。此外，在相对较低的电位下，还可以通过简单的电子转移来开关近红外波段的强度。DFT 研究证实了这些发现。
• Structures, Redox and Spectroscopic Properties of Pd ^II and Pt ^II Complexes Containing an Azo Functionality
  作者：Sayak Roy、Ingo Hartenbach、Biprajit Sarkar

  DOI：10.1002/ejic.200900007

  日期：2009.6

  The complexes [PdCl2(pap)] (1) and [PtCl2(pap)] (2; pap = 2-phenylazopyridine) were synthesized by treating PdCl2 or K2PtCl4, respectively, with pap and characterized by 1H NMR spectroscopy and elemental analysis. Both these complexes, together with the previously reported complex [(az)Pd(μ-Cl)2Pd(az)] (3; az = azobenzene), were also characterized by X-ray crystallography. The structures of 1, 2, and

  配合物 [PdCl2(pap)] (1) 和 [PtCl2(pap)] (2; pap = 2-苯基偶氮吡啶) 是通过分别用 pap 处理 PdCl2 或 K2PtCl4 合成的，并通过 1H NMR 光谱和元素分析进行​​表征。这两种配合物，连同先前报道的配合物 [(az)Pd(μ-Cl)2Pd(az)]（3；az = 偶氮苯），也通过 X 射线晶体学表征。由于金属中心的反向捐赠和配体的未配位部分相对于分子的其余部分的扭曲，1、2和3的结构显示出略微拉长的N-N偶氮双键。1, 2, 3 和相关络合物 [(az)Pt(μ-Cl)2Pt(az)] (4) 的循环伏安法显示还原过程对 1 和 2 是可逆的，但对 3 和 4 是不可逆的。 1 和 2 的还原导致自由基复合物，EPR 光谱显示自旋主要位于配合物的偶氮部分。自由基配合物 2·– 显示出前所未有的 195Pt 超精细耦合常数和此类 PtII
• Roy, Ramakrishna; Das, Debasis; Sinha, Chittaranjan, Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 1998, vol. 37, # 2, p. 141 - 146
  作者：Roy, Ramakrishna、Das, Debasis、Sinha, Chittaranjan

  DOI：——

  日期：——
• Roy, Ramkrishna; Chattopadhyay, Pabitra; Sinha, Chittaranjan, Polyhedron, 1996, vol. 15, p. 3361 - 3370
  作者：Roy, Ramkrishna、Chattopadhyay, Pabitra、Sinha, Chittaranjan、Chattopadhyay, Surajit

  DOI：——

  日期：——