Gao Rui, Liu Zhen, Liu Zeyu, Su Jie, Gan Liangbing
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, People's Republic of China.
J Am Chem Soc. 2023 Aug 16;145(32):18022-18028. doi: 10.1021/jacs.3c05733. Epub 2023 Aug 1.
An open-cage [60]fullerene derivative was prepared through Malaprade oxidation of a vicinal triol moiety as the key step. Above the 17-membered orifice, there is one carboxyl group. Three ketone carbonyl groups and one lactone carbonyl group are located on the rim of the orifice. The carboxylic and carbonyl oxygen atoms around the orifice act as strong polydentate ligands for a sodium ion. These oxygen atoms also react with [Rh(CO)Cl] to form various isomeric rhodium complexes with comparable stability. The fullerene C═C bond on the rim of the orifice forms a stable platinum complex when treated with Pt(PPh). Single crystal X-ray diffraction data reveal that one of the carboxylic oxygen atoms above the orifice forms a H-bond with the water molecule trapped in the cage.
通过邻位三醇部分的马拉普拉德氧化作为关键步骤制备了一种开孔[60]富勒烯衍生物。在17元孔口上方有一个羧基。三个酮羰基和一个内酯羰基位于孔口边缘。孔口周围的羧基和羰基氧原子作为钠离子的强多齿配体。这些氧原子还与[Rh(CO)Cl]反应形成各种具有相当稳定性的异构铑配合物。孔口边缘的富勒烯C═C键在用Pt(PPh)处理时形成稳定的铂配合物。单晶X射线衍射数据表明，孔口上方的一个羧基氧原子与捕获在笼中的水分子形成氢键。
