Functionalization of [60]fullerene through the anionic route

The reactivity of C602- anion, easily generated upon chemical reduction of the C60 core by sodium methanethiolate, has been systematically investigated versus a great number of saturated halogenated compounds RX or X-CH2-R'-CH2-X (X=I or Br), while these halo-compounds are unreactive with C60 itself. Various C60-derivatives in the series of bis-adducts R2C60 and fused cycloadducts R'(CH2)2C60 are thus obtained in fair to good yields, the R or R' groups bearing functionalities such as ethylenic double bond, halogen, ketone, alcohol, or ester moieties. On the other hand a judicious utilization of the overall mechanism of the reaction between C602- anion and well chosen different RX and R'X compounds allow to extend this methodology to the preparation of mixed adducts RR'C60. Functional adducts in the series R2C60 and R'(CH2)2C60 are new attractive building blocks in C60 chemistry, and can lead to novel highly functionalized C60-based molecules. Some examples of such covalent ensembles are presented, the specific physical properties of which are typical of organic materials.