Conjugation-promoted reaction of open-cage fullerene: A density functional theory study
Type
ArticleKAUST Department
Numerical Porous Media SRI Center (NumPor)Smart Hybrid Materials (SHMs) lab
Physical Sciences and Engineering (PSE) Division
Chemical Science Program
Advanced Membranes and Porous Materials Research Center
Date
2012-01-20Permanent link to this record
http://hdl.handle.net/10754/562062
Metadata
Show full item recordAbstract
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. 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.Sponsors
We are grateful to King Abdullah University of Science and Technology (KAUST) for financial support.Publisher
Wiley-BlackwellJournal
ChemPhysChemISSN
14394235PubMed ID
22266747ae974a485f413a2113503eed53cd6c53
10.1002/cphc.201100745
Scopus Count
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