CF ₂ ‐Driven Regioselectivity in C ₇₀ Hydrogenation

We report the theoretical modeling of the reductive hydrogenation of [6,6]-closed, [6,6]-open, and near-equatorial [5,6]-open C₇₀(CF₂)-I-III as well as the regioselective synthesis of three novel C₇₀(CF₂)H₂ isomers I-III, their spectral characterization using mass spectrometry, UV/Vis, FTIR, Raman, and NMR spectroscopy. We have shown that regardless of the configuration of CF₂ moiety and its position at the fullerene cage, the bridgehead carbon atoms are activated in the anionic state and undergone protonation in the presence of water. The regioselectivity of the formation of C₇₀(CF₂)H₂ isomers, as well as unexpected features of suppression of the C₇₀ hydrogenation in the presence of C₇₀(CF₂), and the high reactivity of near-equatorial [5,6]-open C₇₀(CF₂) to polyhydrogenation are discussed from kinetic and thermodynamic aspects.