Evolution of Late Transition‐Metal‐Catalyzed Intermolecular Reductive Coupling Reaction of [60]Fullerene and N‐Sulfonylaldimines: Competing Formation of Hydrobenzylated [60]Fullerenes and 1,2‐Dihydrofullerene

A system based on late transition-metal halides, phosphanes, water, and reducing agents in 1,2-dichlorobenzene can efficiently catalyze the intermolecular reductive coupling of [60]fullerene with N-sulfonylaldimines to afford novel 1,2hydrobenzylated [60]fullerene derivatives. We found that both group VIIB metals (cobalt, rhodium, iridium) and group VIIIB metals (nickel, palladium, platinum) perform this coupling reaction. A control experiment in the absence of aldimines produced C60H2, which showed that the reaction might proceed via a [60]fullerene metal complex [M(η 2 C60)(ligand)]. An isotope labeling experiment with D2 Oa s