Fulleroid addition regiochemistry is driven by pi-orbital misalignment

An investigation into the regiochemistry of addition to the fulleroid C61H2 by Zn(Cu) reduction and hydroboration was conducted. One major isomer is formed by hydroboration while two major isomers of C61H4 were formed by the reduction with Zn(Cu). The structures of the major isomers formed by reduction with Zn(Cu) were identified as 1,2-C6H4 and 3,4-C61H4. The regiochemistry observed in the formation of 1,2-C61H4 was the same regiochemistry seen in the further reactivity of azafulleroids.