Shafie Siham Asyiqin, Nozawa Ryo, Takano Hideaki, Shinokubo Hiroshi
Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering and Integrated Research Consortium Chemical Sciences (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, Japan.
Institute for Advanced Research, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8601, Japan.
Beilstein J Org Chem. 2024 Aug 12;20:1967-1972. doi: 10.3762/bjoc.20.172. eCollection 2024.
Norcorrole is a stable 16π-antiaromatic porphyrinoid that exhibits characteristic reactivities and physical properties. Here, we disclose the reaction of Ni(II) norcorroles with alkyl radicals derived from azo radical initiators. The radical selectively attacked the distal α-position relative to the -position to construct a nonaromatic bowl-shaped structure. The photophysical and electrochemical properties of the obtained radical adducts were compared to those of the parent Ni(II) norcorrole. The radical reactivity of Ni(II) norcorroles was investigated by density functional theory (DFT) calculations.
降卟啉是一种稳定的16π-反芳香性卟啉类化合物，具有独特的反应活性和物理性质。在此，我们揭示了镍（II）降卟啉与偶氮自由基引发剂衍生的烷基自由基的反应。该自由基选择性地进攻相对于β-位的远端α-位，构建了一种非芳香性碗状结构。将所得自由基加合物的光物理和电化学性质与母体镍（II）降卟啉的性质进行了比较。通过密度泛函理论（DFT）计算研究了镍（II）降卟啉的自由基反应活性。
