Conjugation-promoted reaction of open-cage fullerene: A density functional theory study

Handle URI:
http://hdl.handle.net/10754/562062
Title:
Conjugation-promoted reaction of open-cage fullerene: A density functional theory study
Authors:
Guo, Yong; Yan, Jingjing; Khashab, Niveen M. ( 0000-0003-2728-0666 )
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. 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.
KAUST 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
Publisher:
Wiley-Blackwell
Journal:
ChemPhysChem
Issue Date:
20-Jan-2012
DOI:
10.1002/cphc.201100745
Type:
Article
ISSN:
14394235
Sponsors:
We are grateful to King Abdullah University of Science and Technology (KAUST) for financial support.
Appears in Collections:
Articles; Advanced Membranes and Porous Materials Research Center; Physical Sciences and Engineering (PSE) Division; Controlled Release and Delivery Laboratory; Chemical Science Program

Full metadata record

DC FieldValue Language
dc.contributor.authorGuo, Yongen
dc.contributor.authorYan, Jingjingen
dc.contributor.authorKhashab, Niveen M.en
dc.date.accessioned2015-08-03T09:43:51Zen
dc.date.available2015-08-03T09:43:51Zen
dc.date.issued2012-01-20en
dc.identifier.issn14394235en
dc.identifier.doi10.1002/cphc.201100745en
dc.identifier.urihttp://hdl.handle.net/10754/562062en
dc.description.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.en
dc.description.sponsorshipWe are grateful to King Abdullah University of Science and Technology (KAUST) for financial support.en
dc.publisherWiley-Blackwellen
dc.subjectAbramov reactionen
dc.subjectcomputational chemistryen
dc.subjectdensity functional theoryen
dc.subjectfullerenesen
dc.subjectreaction mechanismen
dc.titleConjugation-promoted reaction of open-cage fullerene: A density functional theory studyen
dc.typeArticleen
dc.contributor.departmentNumerical Porous Media SRI Center (NumPor)en
dc.contributor.departmentSmart Hybrid Materials (SHMs) laben
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentAdvanced Membranes and Porous Materials Research Centeren
dc.identifier.journalChemPhysChemen
kaust.authorGuo, Yongen
kaust.authorKhashab, Niveen M.en
kaust.authorYan, Jingjingen
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