title: Conjugation-promoted reaction of open-cage fullerene: a density functional theory study.
abstract: Density functional theory calculations are performed to study the addition mechanism of e-rich moieties such as triethyl phosphite to a carbonyl group on the rim of a fullerene orifice. Three possible reaction channels have been investigated. The obtained results show that the reaction of a carbonyl group on a fullerene orifice with triethyl phosphite most likely proceeds along the classical Abramov reaction; however, the classical product is not stable and is converted into the experimental product. An attack on a fullerene carbonyl carbon will trigger a rearrangement of the phosphate group to the carbonyl oxygen as the conversion transition state is stabilized by fullerene conjugation. This work provides a new insight on the reactivity of open-cage fullerenes, which may prove helpful in designing new switchable fullerene systems.
authors.affiliation: Center of Membrane Porous Materials, Chemical and Life Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal, Kingdom of Saudi Arabia.
authors.forename: Yong
authors.initials: Y
authors.lastname: Guo
authors.forename: Jingjing
authors.initials: J
authors.lastname: Yan
authors.forename: Niveen M
authors.initials: NM
authors.lastname: Khashab