porphyrinatonickel(II) | 15200-33-6

• 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
• 英文名称: porphyrinatonickel(II)
• 英文别名: nickel(II)porphinate；(porphinato)nickel(II)；Ni(II) porphine；nickel-porphyrin complex；nickel porphyrinate；nickel(II) porphyrinate；nickel(II) porphyrin；nickel(II) porphine；nickel porphyrin；nickel porphine；[(5,10,15,20-tetraphenylporphine)Ni]；porphyrin nickel(II)；[Ni(porphyrin)]；Ni(porphyrine)；Ni(porphine)
• CAS: 15200-33-6
• 化学式: C₂₀H₁₂N₄Ni
• 分子量: 367.032
• InChiKey: UMRPTGCMJYVXAU-QDJBTJTOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.91
• 重原子数：
  25.0
• 可旋转键数：
  0.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  53.98
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  porphyrine 、 nickel diacetate 以 氯仿 为溶剂， 生成 porphyrinatonickel(II)
  参考文献：
  名称：

  Vibronic coupling in nickel(II) porphine derived from resonant Raman excitation profiles

  摘要：

  We have measured the resonant Raman excitation profiles of Ni(II) porphine in a CS2 solution for 15 fundamental modes: the A1g modes nu2, nu4, nu6, and nu9; the B1g modes nu10, nu11, nu13, nu15, and nu17; the A2g modes nu19, nu21, nu22, and nu26; and the B2g modes nu29 and nu34. Several Raman lines were found which are indicative of the existence of a second conformer. Three of them correspond to the modeS nu2, nu4, and nu19. The data cover the resonant regions of the Q and the Q(v), bands and the preresonant region of the B band. The depolarization ratio of all lines investigated was found to be independent of the excitation wavelength, in accordance with expectations of a molecule with D4h symmetry. The excitation profiles were first analyzed by use of a theory which describes intra- and interstate coupling in terms of a time-independent perturbation theory (Shelnutt, J. A. J. Chem. Phys. 1981, 74, 6644-6657) in the framework of Gouterman's four-orbital model. This approach accounts for the excitation profiles of all A2g modes and most of the A1g modes, but it fails for all B1g modes and the B2g mode nu34. In a second step, we considered multimode contributions to the scattering process and additional intrastate coupling for the B1g modes within the Q and B states. This yields satisfactory fits to all Raman excitation profiles (REPs), but rather large deviations from the four-orbital model must be assumed. In a third attempt, we took into account possible contributions from a scattering process which involves B1g-type pseudo Jahn-Teller coupling between the porphyrin ground state and a state created by an electron transfer from the d(pi)(Ni) orbital to the e(g) orbital of the porphyrin macrocycle. Thus, it was possible to describe all REPs without relaxation of the restrictions imposed by the four-orbital model. The coupling parameters thus derived are consistent with the absorption spectrum.

  DOI：

  10.1021/j100141a011

文献信息

• Mechanistic Studies on the Nucleophilic Reaction of Porphyrins with Organolithium Reagents
  作者：Xiangdong Feng、Ines Bischoff、Mathias O. Senge

  DOI：10.1021/jo010559x

  日期：2001.12.1

  under formation of phlorin like intermediates which are stable in water. For the Ni(II)phlorins a mesomeric carbanionic form with a highly distorted structure exists that can react as a nucleophile with electrophiles such as RI, H+, or D+. In the latter case a protonation-deprotonation equilibrium involving porphodimethen intermediates has to be assumed. Free base phlorins do not react as nucleophiles but

  卟啉在游离内消旋位置的取代下容易与有机锂试剂反应。由于该方法已证明对于制备各种内消旋取代的卟啉非常通用，因此使用5,15-二芳基和二烷基取代的卟啉2,3,7,8,12对反应进行了机理研究。 ，13,17,18-八乙基卟啉和各自的镍（II）配合物。氘化实验，反应性中间体的电子吸收光谱，中间体与有机亲电子试剂的捕集以及在不同pH值下的反应相结合，表明游离碱卟啉和金属卟啉的反应途径存在显着差异。在这两种情况下，反应最初都是在水中形成稳定的phlorin样中间体的形成下进行的。对于Ni（II）卟啉，存在具有高度扭曲结构的中观碳负离子形式，可以作为亲核体与亲电体（如RI，H +或D +）反应。在后一种情况下，必须假定涉及卟啉二甲醚中间体的质子化-去质子化平衡。游离碱发菲林不作为亲核试剂反应，但可以在强酸性介质中进行H / D交换反应。
• Simulation of Non-Condon Enhancement and Interference Effects in the Resonance Raman Intensities of Metalloporphyrins
  作者：Ranjit Kumble、Thomas S. Rush、Milton E. Blackwood、Pawel M. Kozlowski、Thomas G. Spiro

  DOI：10.1021/jp9811225

  日期：1998.9.1

  The room-temperature resonance Raman (RR) spectra of nickel(IT) porphine have been simulated for excitation within the Q-band optical transition, taking into account both coordinate-independent (Condon) as well as coordinate-dependent (non-Condon) contributions to the Raman scattering amplitude of each vibration. Computation of scattering intensities for all three classes of Raman-active modes (polarized, depolarized, and inversely polarized) observed in metalloporphyrin spectra was made possible in this fashion. Vibronic parameters were evaluated at the INDO level from the dependence of electronic transition moments and transition energies upon nuclear coordinates; the transform theory of RR scattering was then applied to compute the relative intensities of vibrational modes. The calculated enhancement patterns are in excellent agreement with experimental results. Three vibrational modes of b(1g) symmetry (upsilon(10), upsilon(11), and upsilon(16)) are identified as being the primary Jahn-Teller distortion coordinates: a substantial fraction of the total internal-mode reorganization energy for S-0 - S-1 photoexcitation is predicted to arise from symmetry-lowering. Interference between Condon and non-Condon scattering amplitudes is found to be a major determinant of the intensities of several polarized vibrations as well as those depolarized modes which are Jahn-Teller active. The dependence of scattering intensity on excitation wavelength for such modes is correctly predicted, indicating that the relative amplitudes and phasing of Condon and non-Condon contributions for each vibration are reliably determined.