(octaethylporphyrinato)palladium(II) | 24804-00-0

• 物质功能分类: 催化剂及助剂 - 贵金属催化剂
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: (octaethylporphyrinato)palladium(II)
• 英文别名: palladium(II) octaethylporphyrin；2,3,7,8,12,13,17,18-octacetyl-21H,23H-porphyrin palladium(II)；PdOEP
• CAS: 24804-00-0
• 化学式: C₃₆H₄₄N₄Pd
• 分子量: 639.192
• InChiKey: FVPOYVGWFFRIHG-XTPDIVBZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.28
• 重原子数：
  41.0
• 可旋转键数：
  8.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  53.98
• 氢给体数：
  0.0
• 氢受体数：
  2.0

安全信息

• WGK Germany：
  3

反应信息

• 作为反应物：
  描述：

  (octaethylporphyrinato)palladium(II) 在 tris-(4-bromophenyl)aminium hexachloroantimonate 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以76%的产率得到
  参考文献：
  名称：

  Metalloporphyrin Mixed-Valence π-Cation Radicals:  Solution Stability and Properties

  摘要：

  Solution equilibria and optical spectra of several metallooctaethylporphyrin pi-cation radicals have been examined in methylene chloride solution. The several pi-cation radical species, [M(OEP(.))]Y (M = Cu, Ni, Zn, Pd, or VO; Y = ClO4- or SbCl6-), are found to dimerize to form [M(OEP(.))](2)(2+). These dimeric species are characterized by the appearance of a new, strongly concentration-dependent near-infrared absorption band. This band is found in the region of 900-960 nm for all compounds except for the vanadyl complex which absorbs farther to the red at 1375 nm. The equilibrium constants for the dimerization reaction (2[M(OEP(.))](+) (K-D) [M(OEP(.))](2)(2+)) have been evaluated from multiple-wavelength concentration-dependent absorption data. Equimolar solutions of these pi-cation radicals and their analogous neutral M(OEP) derivatives react to form new binuclear species, [M(OEP(./2))](2)(+), in which the single radical electron is delocalized over both porphyrin rings. These new species, for which we suggest the term ''mixed-valence'' pi-cation radical and which bear a formal relationship to the oxidized special pair of photosynthetic reaction centers, also display a near-infrared absorption band. The near-IR band is however distinctly different from that of the pi-cation radical dimers. Equilibrium constants for the formation of these new species (M(OEP) + [M(OEP(.))](+) (K-MV) [M(OEP(./2))](2)(+)), have also been determined. The values of K-MV are 10-100-fold larger than the analogous dimerization constant K-D. Values of Delta H and Delta S have been obtained for both equilibrium processes. The variations in K-MV and K-D values are largely the consequence of entropy differences that probably result from a much stronger solvation of the pi-cation radical compared to the neutral porphyrin.

  DOI：

  10.1021/ja9616950
• 作为产物：
  描述：

  以 二氯甲烷 为溶剂， 生成 (octaethylporphyrinato)palladium(II) 、
  参考文献：
  名称：

  Metalloporphyrin Mixed-Valence π-Cation Radicals:  Solution Stability and Properties

  摘要：

  Solution equilibria and optical spectra of several metallooctaethylporphyrin pi-cation radicals have been examined in methylene chloride solution. The several pi-cation radical species, [M(OEP(.))]Y (M = Cu, Ni, Zn, Pd, or VO; Y = ClO4- or SbCl6-), are found to dimerize to form [M(OEP(.))](2)(2+). These dimeric species are characterized by the appearance of a new, strongly concentration-dependent near-infrared absorption band. This band is found in the region of 900-960 nm for all compounds except for the vanadyl complex which absorbs farther to the red at 1375 nm. The equilibrium constants for the dimerization reaction (2[M(OEP(.))](+) (K-D) [M(OEP(.))](2)(2+)) have been evaluated from multiple-wavelength concentration-dependent absorption data. Equimolar solutions of these pi-cation radicals and their analogous neutral M(OEP) derivatives react to form new binuclear species, [M(OEP(./2))](2)(+), in which the single radical electron is delocalized over both porphyrin rings. These new species, for which we suggest the term ''mixed-valence'' pi-cation radical and which bear a formal relationship to the oxidized special pair of photosynthetic reaction centers, also display a near-infrared absorption band. The near-IR band is however distinctly different from that of the pi-cation radical dimers. Equilibrium constants for the formation of these new species (M(OEP) + [M(OEP(.))](+) (K-MV) [M(OEP(./2))](2)(+)), have also been determined. The values of K-MV are 10-100-fold larger than the analogous dimerization constant K-D. Values of Delta H and Delta S have been obtained for both equilibrium processes. The variations in K-MV and K-D values are largely the consequence of entropy differences that probably result from a much stronger solvation of the pi-cation radical compared to the neutral porphyrin.

  DOI：

  10.1021/ja9616950

文献信息

• Transformations of<i>meso</i>-Iminofunctionalized Pd(II) and Ni(II)-Complexes of β-Alkylsubstituted Porphyrins
  作者：Dina R. Erzina、Ilya A. Zamilatskov、Nadezhda M. Stanetskaya、Vladimir S. Tyurin、Grigory L. Kozhemyakin、Gelii V. Ponomarev、Vladimir V. Chernyshev、Andrew N. Fitch

  DOI：10.1002/ejoc.201801659

  日期：2019.2.21

  New types of meso‐functionalization of porpyrins through formylation, Schiff base formation followed by thermal annulation or base treatment leading to cyclopentane‐condensed or meso‐cyano‐, meso‐amido‐, and meso‐hydroxy‐porphyrins.

  通过甲酰化，席夫碱形成，随后的热成环或碱处理，使卟啉具有新型的介孔功能化，从而导致环戊烷缩合或介氰基，介酰氨基和介羟基羟基卟啉。
• Structural modification and kinetic stability of octaethylporphyne complexes with palladium (II)
  作者：T. N. Lomova、M. E. Klyueva、E. Yu. Tyulyaeva

  DOI：10.1134/s0036024411060215

  日期：2011.6

  mono-meso-phenyl derivative), the complexes undergo transformations that are investigated by chemical kinetics. It is shown that instead of the usual dissociation of the coordination center, single-electron oxidation in the macrocycle of complexes takes place. A multistage mechanism is revealed that involves the kinetically significant equilibrium between the formation of H-associated complex and irreversible coordination

  比较2,3,7,8,12,13,17,18-八乙基-21H，23H-卟啉（H 2 OEP）中逐步取代内消旋苯基对与其Pd（II）配合物稳定性的影响到内消旋-tetraphenylporphyne复合物与未取代的C β原子被化学动力学和物理化学分析来调查。使用光谱方法，研究了ACOH -H 2 SO 4混合物中配合物的状态和反应，以了解广泛的组成。结果发现，配位中心在混合物中的H 2 SO 4含量高达100％时是稳定的。无论是在分子状态或与质子（和的PdOEP其单关联的内消旋-苯基衍生物），复合物经历由化学动力学研究转化。结果表明，配合物的大环中发生单电子氧化，而不是配位中心的通常解离。揭示了一种多级机理，涉及在H-缔合的配合物的形成与分子氧的不可逆配位之间的动力学上显着的平衡，然后是电子将其从芳族体系转移到该氧的酸辅助转移。确定了配合物的氧化稳定性，讨论了大环配体结构与配位中心电子结构之间的关系。
• Effect of the chemical modification of the tetrapyrrole macrocycle on the reactivity of porphyrins in complexation with Pt4+ and Pd2+ cations
  作者：N. V. Chizhova、N. Zh. Mamardashvili

  DOI：10.1134/s0036023607020180

  日期：2007.2

  The reactions of 5,10,15,20-tetraphenylporpine, 5,10,15-triphenyl-20-(4-hexadecanoxyphenyl)porphine, 5,10,15,20-tetra-(4-butoxyphenyl)porphine, and 2,3,7,8,12,13,17,18-ocaethylporphine with H2PtCl6 in boiling phenol and with PdCl2 in boiling dimethylformamide are studied by spectrophotometry. Due to a strong electronic effect of the substituents, the reactivity of the tetrapyrrole macrocycle during porphyrinate formation changes by more than two orders of magnitude. Platinum(II) 5,10,15-triphenyl-20-(4-hexadecanoxyphenyl)porphinate and palladium(II) 5,10,15,20-tetra-(4-butoxyphenyl)porphinate have been synthesized and identified for the first time.
• Stolzenberg, Alan M.; Schussel, Leonard J., Inorganic Chemistry, 1991, vol. 30, # 16, p. 3205 - 3213
  作者：Stolzenberg, Alan M.、Schussel, Leonard J.

  DOI：——

  日期：——
• The kinetics of disproportionation of hydrogen peroxide in the presence of palladium(II)porphyrins with regularly changing macroring structures
  作者：T. N. Lomova、M. E. Klyueva、O. V. Kosareva、M. V. Klyuev

  DOI：10.1134/s0036024408070066

  日期：2008.7

  The kinetics and spectral manifestations of alkaline decomposition of H2O2 in a water-dimethylformamide medium catalyzed by (PdP)-P-II (P is the dianion of octaethylporphyrin and its monophenyl, 5,15-diphenyl,5,10-diphenyl, triphenyl, and tetraphenyl derivatives substituted at meso positions) was studied over a wide range of reagent concentrations under polythermal conditions. A complete kinetic description of the reacting systems was given, and the rates and set of elementary reactions, intermediate compounds, and kinetically significant equilibria were determined. The ion-molecular mechanism of hydrogen peroxide decomposition was substantiated. According to this mechanism, the only stable radicals involved in the reaction are the pi radical cation forms of palladium(II)porphyhrin catalysts.

表征谱图