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J Am Chem Soc. 2007 Dec 26;129(51):16149-62. Epub 2007 Dec 1.

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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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, China.


Fullerene 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.

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