Dithiolation of [70]Fullerene with Aliphatic Primary Thiols in the Presence of n-Butylamine via Aerobic Oxidation Reaction.

Aerobic oxidation reaction of [70]fullerene with aliphatic primary thiols in the presence of n-butylamine was studied. The reaction afforded both the fullerene dithiol (2) and dithiol epoxide (3) compounds, which were characterized by 1H and 13C NMR, HRMS and UV-vis spectroscopies. In situ vis-NIR spectral measurement showed absorption bands due to anionic fullerene species, indicating that the reaction was likely initiated with the addition of thiolate anions to C70. Computational calculations were performed to rationalize the structure of the dithiol epoxide compounds. The electrochemical property of 2,5-( n-C5H11S)2C70 (2a) was compared with two analogue compounds of 2,5-Bn2C70 and 2-MeO-5-BnC70 that had identical addition pattern and number of addends. The result showed that the dithiol compound was more electron deficient than the other two derivatives.