Hydro-aza-(C59 N)fullerenes: Formation Mechanism and Hydrogen Substitution.

Azafullerenes are as yet the only synthetically available heterofullerenes. Herein, we present plausible reaction pathways towards pentaaryl azafullerenes, focusing on the reactivity of hydro-azafullerene intermediates and their regiochemistry. The X-ray structure of a β'-hydro-tetraaryl adduct is presented for the first time. The reactivity of dihydro-azafullerene adducts is demonstrated here through H-abstraction in mass spectrometric experiments. Moreover, hydride abstraction and subsequent hydroxylation is possible, as well as deprotonation followed by alkylation.