Total Synthesis of Buckminsterfullerene (C60) and Endohedral Metal Complexes

A summary of our work aimed at the synthesis of a variety of endohedral metal complexes of fullerenes is presented. The completion of the synthesis of suitable highly unsaturated macrocyclic precursors containing 60 carbon atoms is described. These compounds were required to study their rearrangement to a fullerene framework in a process analogous to the gas-phase rearrangement of mono- and polycyclic polyynes acetylenic rings in the formation of C60 and higher fullerenes. Three types of synthetic acetylenic precursors were targeted, namely triply-linked bis-benzene-cyclophanes with octayne linking units, sextuply-linked bis-benzene-cyclophanes with tetrayne linkers, and deca-alkynylated metallocenes which include a metal in their structure early in the synthesis. The rearrangement to C60 of the first examples of these compounds has been studied in the gas phase by LDMS and in solution by various chemical reactions. Another aspect of our work was initiated by the successful opening of the largest orifice on the framework of C60 known to date in the form of a cobaltIII complex of ethenobisfulleroid C64H4. This strategy is being applied in a double fashion on adjacent sites of the surface of C60 to form an even larger opening, aimed at eventual metal insertion inside the cage.