Fullerene‐Based Macro‐Heterocycle Prepared through Selective Incorporation of Three N and Two O Atoms into C60

A 14‐membered heterocycle is created on the C₆₀ cage skeleton through a multistep procedure. Key steps involve repeated PCl₅‐induced hydroxylamino N?O bond cleavage leading to insertion of nitrogen atoms, and also piperidine‐induced peroxo O?O bond cleavage leading to insertion of oxygen atoms. The hetero atoms form one pyrrole, two pyran, and one diazepine rings in conjunction with the C₆₀ skeleton carbon atoms. The fullerene‐based macrocycle showed unique reactivities towards fluoride ion and copper salts.     

Fullerenyl azide: synthesis and reactivity

Trimethylsilyl azide adds to the carbonyl carbon in a cage-opened fullerene derivative to form the first fullerenyl azide compound. The fullerene-bound azido group exhibits some unusual reactivity compared with that exhibited by other organic azido compounds. Heating the azidofullerene at 100 °C only led to the cleavage of peroxo groups in the compound, whereas the azido group remained unchanged. Triphenylphosphine reacted with the azido group to form isolable iminophosphorane, which could not be hydrolyzed under normal acidic and basic conditions.