ja0763798_si_005.cif (28.5 kB)
Download fileSynthesis of [59]Fullerenones through Peroxide-Mediated Stepwise Cleavage of Fullerene Skeleton Bonds and X-ray Structures of Their Water-Encapsulated Open-Cage Complexes
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posted on 2007-12-26, 00:00 authored by Zuo Xiao, Jiayao Yao, Dazhi Yang, Fudong Wang, Shaohua Huang, Liangbing Gan, Zhenshan Jia, Zhongping Jiang, Xiaobing Yang, Bo Zheng, Gu Yuan, Shiwei Zhang, Zheming WangFullerene skeleton modification has been investigated through selective cleavage of the fullerene
carbon−carbon bonds under mild conditions. Several cage-opened fullerene derivatives including three
[59]fullerenones with an 18-membered-ring orifice and one [59]fullerenone with a 19-membered-ring orifice
have been prepared starting from the fullerene mixed peroxide 1, C60(OOtBu)6. The prepositioned tert-butyl peroxy groups in 1 serve as excellent oxygen sources for formation of hydroxyl and carbonyl groups.
The cage-opening reactions were initiated by photoinduced homolysis of the tBu−O bond, followed by
sequential ring expansion steps. A key step of the ring expansion reactions is the oxidation of adjacent
fullerene hydroxyl and amino groups by diacetoxyliodobenzene (DIB). Aminolysis of a cage-opened fullerene
derivative containing an anhydride moiety resulted in multiple bond cleavage in one step. A domino
mechanism was proposed for this reaction. Decarboxylation led to elimination of one carbon atom from
the C60 cage and formation of [59]fullerenones. The cage-opened [59]fullerenones were found to encapsulate
water under mild conditions. All compounds were characterized by spectroscopic data. Single-crystal
structures were also obtained for five skeleton-modified derivatives including two water-encapsulated
fulleroids.