4-tert-butylcatecholato-(2-(phenylazo)pyridine)platinum(II) | 341495-15-6

• 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: 4-tert-butylcatecholato-(2-(phenylazo)pyridine)platinum(II)
• 英文别名: Pt(phenylazopyridine)((4-tert-butylcatecholate)；Pt(pap)(O2C6H3(Bu-t))
• CAS: 341495-15-6；1338818-16-8；1338818-33-9
• 化学式: C₂₁H₂₁N₃O₂Pt
• 分子量: 542.497
• InChiKey: AYNMXEKNSAHIBC-QDBORUFSSA-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：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  苯基(吡啶-2-基)二氮烯 在 triethylamine 作用下， 以 甲醇 、 氯仿 、 水 、 乙腈 为溶剂， 生成 4-tert-butylcatecholato-(2-(phenylazo)pyridine)platinum(II)
  参考文献：
  名称：

  Synthesis, spectral characterization and electrochemical studies of mixed-ligand complexes of platinum(II) with 2-(arylazo)pyridines and catechols. Single-crystal X-ray structure of dichloro{2-(phenylazo) pyridine}platinum(II)

  摘要：

  The reaction of 2-(arylazo)pyridines, RH4C6N=NC5H4N (aap, 1 where R=H (pap), p-Me (p-tap), p-Cl (p-Clpap)) with K2PtCl4 in 1:2 boiling acetonitrile-water affords orange-red complexes of the type Pt(aap)Cl-2 (2). The IR spectrum shows two v(Pt-Cl) stretches suggesting cis-PtCl2 configuration. The structural confirmation was carried out by an X-ray diffraction study of Pt(pap)Cl-2 (2a). The addition of catechols to a chloroform-methanol solution of Pl(aap)Cl-2 in the presence of Et3N yielded green colored mixed-ligand complexes of the formula Pt(aap)(O,O) (O,O = catecholate (cat) (3), 4-tert-butylcatecholate (tbcat), (4), 3,5-di-tert-butylcatecholate (dtbcat) (5) and tetrachlorocatecholate (tccat) (6)). The complexes were characterized by elemental analyses, IR, W-Vis-NIR and H-1 NMR spectral data. Electronic spectra exhibit a ligand-ligand charge transfer (LLCT) transition at NIR region; the position and symmetry of the band depend on the type of substituent on the catechol frame. This is qualitatively assigned as 3b(1)(cat)-->pi*(aap) transition. Cyclic voltammogram of the complexes show four successive redox responses: two couples positive to SCE are referred to as oxidation of catechol to semiquinone and semiquinone to quinone, respectively and two couples negative to SCE correspond to azo reductions. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0277-5387(00)00530-1

文献信息

• 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。