Conjugation-promoted reaction of open-cage fullerene: A density functional theory study
KAUST DepartmentAdvanced Membranes and Porous Materials Research Center
Biological and Environmental Sciences and Engineering (BESE) Division
Chemical Science Program
Numerical Porous Media SRI Center (NumPor)
Physical Sciences and Engineering (PSE) Division
Smart Hybrid Materials (SHMs) lab
Permanent link to this recordhttp://hdl.handle.net/10754/562062
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AbstractDensity 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. Not that classical: The reaction of a carbonyl group on the fullerene orifice with triethyl phosphite most likely proceeds following the Abramov reaction to firstly form a classical product. However, this product is not stable and turns into an experimental product as the conversion transition state is stabilized by fullerene conjugation (see picture). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
SponsorsWe are grateful to King Abdullah University of Science and Technology (KAUST) for financial support.
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