Pressure effect on heterogeneous trifluoromethylation of fullerenes and its application

The first systematic study of heterogeneous fullerene trifluoromethylation using an innovative gradient-temperature gas–solid reactor revealed a significant effect of CF3I pressure on the conversion of C60 and C70 into trifluoromethylated products and on the range of fullerene(CF3)n compositions that were obtained. The design of the reactor allowed us to lower the residence times of fullerene(CF3)n species in the hot zone which resulted in the significant differences in relative isomeric distributions as compared to the earlier methods. For the first time, gram quantities of trifluoromethylated fullerenes were prepared using the new reactor, and the selective synthesis of a single-isomer C60(CF3)2 was developed. The relative reactivity of C70 as a CF3 radical scavenger was found to be much lower than that of C60, especially at an early radical addition stage, which led to the cost-efficient synthesis of C60(CF3)2 from a fullerene extract.