5,10,23-三（均三甲苯基）[28]七卟啉（1.1.0.0.1.0.0）的双钯配合物前所未有的强顺磁环电流。
The unprecedented strong paratropic ring current of a bis-Pd complex of 5,10,23-trimesityl [28]heptaphyrin(1.1.0.0.1.0.0).
作者信息
Liu Yang, Xu Ling, Jin Xiaorong, Yin Bangshao, Rao Yutao, Zhou Mingbo, Song Jianxin, Osuka Atsuhiro
机构信息
Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University Changsha 410081 China
出版信息
Chem Sci. 2024 Jun 7;15(29):11402-11407. doi: 10.1039/d4sc01909a. eCollection 2024 Jul 24.
Acid-catalyzed Friedel-Crafts-type cyclization of tetrapyrrolic BF complex 1 and α,α'-dibromotripyrrin 2 gave 5,10,23-trimesityl [28]heptaphyrin(1.1.0.0.1.0.0) BF complex 3BF as a stable and moderate antiaromatic macrocycle. Demetalation of 3BF with methanesulfonic acid followed by treatment with HCl gave free-base salt 3HCl that holds a chloride anion at the core. This salt displays a planar structure with an inverted pyrrole and a stronger paratropic ring current. Metalation of neutral free-base 3 with PdCl gave bis-Pd complex 3Pd as a stable antiaromatic molecule. The H NMR spectrum of 3Pd displays signals due to pyrrolic β-protons in the range of -1.06 ∼ -1.90 ppm, indicating the unprecedented strong paratropic ring current.
四吡咯硼酸配合物1与α,α'-二溴三吡咯2的酸催化傅克型环化反应生成了5,10,23-三均三甲苯基[28]七卟啉(1.1.0.0.1.0.0)硼酸配合物3BF，它是一种稳定的中等反芳香性大环化合物。用甲磺酸对3BF进行脱金属处理，随后用盐酸处理，得到了在核心处含有氯离子阴离子的游离碱盐3HCl。该盐呈现出一种具有倒置吡咯和更强抗磁环电流的平面结构。用PdCl对中性游离碱3进行金属化反应得到双钯配合物3Pd，它是一种稳定的反芳香性分子。3Pd的1H NMR谱在-1.06 ∼ -1.90 ppm范围内显示出由于吡咯β-质子产生的信号，表明存在前所未有的强抗磁环电流。
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