title: Amination of [60]fullerene by ammonia and by primary and secondary aliphatic amines--preparation of amino[60]fullerene peroxides.
abstract: Ammonia and aliphatic amines react readily in the oxygen-rich regions of the Cs symmetric fullerene peroxides C60(O)(OOtBu)4 (1) and C60(OH)(Br)(OOtBu)4 (2 c). Michael addition-type hydroamination of the 1,4-diene moiety on the central skew-pentagon was observed when 1 was treated with ammonia or with nonbulky primary amines, while sterically demanding primary amines opened the epoxy moiety to form vicinal aminohydroxy fullerene compounds with the amino group on the central pentagon. In 2 c the bromo group was replaced under similar conditions by ammonia and primary amines. Cyclic secondary amines showed different reaction patterns, forming hydrogenation products or aminoketal-fullerenes when treated with 1 and 2 c, respectively. Single-electron transfer (SET) is the key step in all the proposed mechanisms. The compounds were characterized by their spectroscopic data, and in addition, three single-crystal X-ray structures were obtained.
authors.affiliation: Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory Organic Solids, Chinese Academy of Science, Institute Chemistry, Beijing, 100080, China.
authors.forename: Xiangqing
authors.initials: X
authors.lastname: Hu
authors.forename: Zhongping
authors.initials: Z
authors.lastname: Jiang
authors.forename: Zhenshan
authors.initials: Z
authors.lastname: Jia
authors.forename: Shaohua
authors.initials: S
authors.lastname: Huang
authors.forename: Xiaobing
authors.initials: X
authors.lastname: Yang
authors.forename: Yuliang
authors.initials: Y
authors.lastname: Li
authors.forename: Liangbing
authors.initials: L
authors.lastname: Gan
authors.forename: Shiwei
authors.initials: S
authors.lastname: Zhang
authors.forename: Daoben
authors.initials: D
authors.lastname: Zhu