Synthesis of Imino[60]fullerenes Using Nitriles and Trimethylsilylmethyl Triflate

The synthesis of a new class of fullerene derivatives, 1-imino-4-silylmethyl[60]fullerene derivatives, is described. The anion (C60R1−) of an alkyl- or aryl-adduct of [60]fullerene, C60R1H (R1 = CH2SiMe3, CH2SiMe2Ph, C6H4−OMe-4, C6H4−NMe2-4, C6H4−CF3-4 and C6H4−OMe-2), was allowed to react with a nitrilium salt [R2CNCH2SiMe3][OTf] (Tf = SO2CF3) that was generated in situ by the reaction of Me3SiCH2OTf and a nitrile solvent R1CN (R2 = Ph and Me). The desired imino[60]fullerene derivative C60(R1) [C(=NCH2SiMe3)R2] was produced in a yield up to 80%. The structure of the product with R1 = C6H4−OMe-4 and R2 = Ph was determined by single-crystal X-ray analysis.