Fullerene peroxides in cage-opening reactions

Fullerene-mixed peroxides C-60(O)(OO'Bu)(4) and C-60((OOBu)-Bu-t)(6) are effective precursors for cage-opened fullerene derivatives. Lewis acids induce the heterolysis of peroxo O-O bond in C-60(O)((OOBu)-Bu-t)(4). Subsequent Hock-type rearrangement affords both [5,6]- and [6,6]-fullerene hemiketals-oxahomofullerene. Photolysis of C-60((OOBu)-Bu-t)(6) results in the homolysis of O-O and C-O bonds, affording fullerene diketone as the major product. Spectroscopic data and single-crystal analysis confirmed the cage-opening reactions.