| 156025-37-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• CAS: 156025-37-5
• 化学式: C₃₆H₄₈N₄Ni
• 分子量: 595.494
• InChiKey: GIBQBZNADOVWPV-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：

  在 甲基锂 作用下， 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Metal-Mediated Transfer of Electrons between Two Different C−C Single Bonds That Function as Electron-Donor and Electron-Acceptor Units

  摘要：

  DOI：

  10.1002/(sici)1521-3773(20000502)39:9<1685::aid-anie1685>3.0.co;2-q
• 作为产物：
  描述：

  在 I₂ 作用下， 以 四氢呋喃 为溶剂， 以79%的产率得到
  参考文献：
  名称：

  Metal-Mediated Transfer of Electrons between Two Different C−C Single Bonds That Function as Electron-Donor and Electron-Acceptor Units

  摘要：

  DOI：

  10.1002/(sici)1521-3773(20000502)39:9<1685::aid-anie1685>3.0.co;2-q

文献信息

• One- and Two-Electron Oxidative Pathways Leading to Cyclopropane-Containing Oxidized Porphyrinogens and C−C-Coupled Porphyrinogens from Alkali Cation− and Transition Metal−<i>meso</i>-Octaethylporphyrinogen Complexes
  作者：Raffaella Crescenzi、Euro Solari、Carlo Floriani、Angiola Chiesi-Villa、Corrado Rizzoli

  DOI：10.1021/ja982178f

  日期：1999.3.1

  This report deals with the different transition metal- and alkali cation-assisted oxidation pathways of the meso-octaethylporphyrinogen tetraanion [Et8N4](4-). The two-electron oxidation of [Et8N4MnNa(thf)(2)}(2)], 4, with Cp2FeBPh4 led to the corresponding monocyclopropane derivative [Et8N4(Delta)Mn], 6, [Delta = cyclopropane], while the one-electron oxidation with CuCl2 or O-2 led to the Mn(III)-porphyrinogen [Et8N4Mn][Li(thf)(4)], 5, which can be further oxidized by an excess of CuCl2 to [Et8N4(Delta)(2)Mn-Cl](+)[Cu9Cl11](0.5), 7. The formation of 7 does not follow the expected sequence Mn(II) --> Mn(III) --> Mn(II)-monocyclopropane --> Mn(II) - biscyclopropane-porphyrinogen. In the case of iron(II)-porphyrinogen, [Et8N4FeLi(thf)(2)}(2)], 9, the oxidation led in a preliminary stage to the iron(III) derivative [Et8N4Fe][Li(thf)(4)], 10, then to the metalated form of the biscyclopropane-porphyrinogen [Et8N4(Delta)(2)Fe-Cl]mu-Cu4Cl5}], 11. The supposed stabilization of the biscyclopropane by the copper(I) cluster was ruled out by carrying the oxidation of [Cy4N4FeLi(thf)(2)}(2)], 11, to [Cy4N4(Delta)(2)Fe-Cl][Cu2Cl4], 14. The stepwise oxidation of [Et8N4M(thf)(4)] [M = Li, 1; M = Na, 2] with Cp2FeBPh4 led to [Et8N4(Delta)Li(2)thf(2)], 15, [Et8N4(Delta)Li]BPh4, 16, and [Et8N4(Delta)Na]BPh4, 17. The reaction of 1 with 16 leading to 15 showed how the C-C moiety in cyclopropane can be engaged in an intermolecular electron transfer. The reaction of 17 with 18-crown-6 allowed the release of biscyclopropane-porphyrinogen [Et8N4(Delta(2))] Particularly interesting is the thermal rearrangement of 15 to 19 occurring via intra- and intermolecular electron transfers with the transposition of the C-C bond of the cyclopropane to a C-C bridge across the beta position of two adjacent pyrroles. In the case of metals, such as Ni(II), which do not undergo oxidation state changes, the primary oxidation product of a metalla-meso-octaalkylporphyrinogen is the monocyclopropane derivative, which reacting with the starting material masks an overall one-electron oxidation. In fact, the reaction of [Et8N4NiLi(thf)(2)}(2)], 20, with 2 equiv of Cp2FeBPh4 led to the expected [Et8N4(Delta)Ni], 21, while the reaction of 20 with 1 equiv of Cp2FeBPh4 led to the dimer [(beta-beta)(Et8N4)(2)Ni-2], 22, which forms equally well from the reaction of 20 and 21. Complex 22 is a quite unique metallaporphyrinogen dimer, where the two monomeric units are joined via a C-C bond in the beta position of a pyrrole. Such a reaction shows that the methodology can accede to oligomeric forms of metallaporphyrinogens.
• meso-Octaethylporphyrinogen Displaying Site Selectivity in the Stepwise Synthesis of Polymetallic Aggregates with Interesting Redox Properties: The π-Binding Ability of Metalla-Porphyrinogens
  作者：Lucia Bonomo、Euro Solari、Mario Latronico、Rosario Scopelliti、Carlo Floriani

  DOI：10.1002/(sici)1521-3765(19990702)5:7<2040::aid-chem2040>3.0.co;2-4

  日期：1999.7.2

  The present report deals with the synthetic approach to homo- and heteronuclear polymetallic aggregates using the Ni-II-meso-octaethylporphyrinogen complex [eta(3)-(Et8N4Ni)}Li(thf)(2)}(2)] (1) as a pi ligand in the reaction with metal halides. The metallation reaction occurs via the probable intermediate of an isomeric form of 1, namely 2, which should be considered an organolithium derivative. Among the polymetallic aggregates, complexes [eta(5)-(Et8N4Ni)}(2)Co]. 2[Li(thf)(4)] (6) and [eta(2)-eta(4)-(Et8N4Ni)}(2)Ni-2(mu-Cl)][Li(thf)] (8) display a thermal and photochemical lability. Electron transfer reactions can be photochemically or thermally induced resulting in the formation of metal(0) and oxidized forms of the meso-ctaethylporphyrinogen skeleton.