Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi, 464-8603, Japan.
Angew Chem Int Ed Engl. 2017 Sep 18;56(39):11822-11825. doi: 10.1002/anie.201706134. Epub 2017 Aug 16.
The synthesis of a bowl-shaped antiaromatic molecule was achieved through the deformation of a planar antiaromatic porphyrinic π-conjugation system by insertion of palladium into the small cavity of a metal-free norcorrole. The bowl-to-bowl inversion dynamics of the antiaromatic Pd-coordinated norcorrole was determined by variable-temperature H NMR spectroscopy. The metal-free norcorrole was prepared from acid-induced demetalation of a copper norcorrole, which was obtained from the intramolecular coupling of a bis(diiododipyrrin) copper complex with copper thiophenecarboxylate.
通过将钯插入无金属 norcorrole 的小空腔中，实现了碗状反芳香分子的合成，从而使平面反芳香卟啉π共轭体系变形。通过变温 H NMR 光谱确定了反芳香 Pd 配位 norcorrole 的碗到碗反转动力学。无金属 norcorrole 是通过酸诱导脱金属铜 norcorrole 制备的，铜 norcorrole 是由双（二碘二吡咯）铜配合物与铜噻吩羧酸酯的分子内偶联得到的。
