Synthesis 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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• 作者：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 Wang
• 刊名：Journal of the American Chemical Society
• 出版年：2007
• 出版时间：December 26, 2007
• 年：2007
• 卷：129
• 期：51
• 页码：16149 - 16162
• 全文大小：560K
• 年卷期：v.129,no.51(December 26, 2007)
• ISSN：1520-5126

文摘

Fullerene skeleton modification has been investigated through selective cleavage of the fullerenecarbon-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 orificehave been prepared starting from the fullerene mixed peroxide 1, C₆₀(OO^tBu)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 bysequential ring expansion steps. A key step of the ring expansion reactions is the oxidation of adjacentfullerene hydroxyl and amino groups by diacetoxyliodobenzene (DIB). Aminolysis of a cage-opened fullerenederivative containing an anhydride moiety resulted in multiple bond cleavage in one step. A dominomechanism was proposed for this reaction. Decarboxylation led to elimination of one carbon atom fromthe C₆₀ cage and formation of [59]fullerenones. The cage-opened [59]fullerenones were found to encapsulatewater under mild conditions. All compounds were characterized by spectroscopic data. Single-crystalstructures were also obtained for five skeleton-modified derivatives including two water-encapsulatedfulleroids.