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Enantiospecific cis-trans isomerization in chiral fulleropyrrolidines: Hydrogen-bonding assistance in the carbanion stabilization in H2O@C60

The stereochemical outcome of cis-trans isomerization of optically pure [60], [70], and endohedral H2O@C60 fulleropyrrolidines reveals that the electronic nature of substituents, fullerene size, and surprisingly the incarcerated water molecule plays a crucial role in this rearrangement process. Theoretical DFT calculations are in very good agreement with the experimental fi ndings. On the basis of the experimental results and computational calculations, a plausible reaction mechanism involving the hydrogen-bonding assistance of the inner water molecule in the carbanion stabilization of endofullerene is proposed

Financial support by the European Research Council (ERC-320441-Chirallcarbon and FP7-PEOPLE-2013-CIG-630978 to S.O.), the Ministerio de Economia y Competitividad (MINECO) of Spain (projects CTQ2011-24652/BQU and CTQ2011-23156/BQU, JdlC contract to S.O, and AP2010-2517 to M.G.-B.), the CAM (PHOTOCARBON project S2013/MIT-2841), the Generalitat de Catalunya (project number 2014SGR931 and ICREA Academia 2009 to M.S.) is acknowledged. N.M. thanks to the Alexander von Humboldt Foundation

American Chemical Society (ACS)

Manager: Ministerio de Ciencia e Innovación (Espanya)
Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca
Author: Maroto, Enrique E.
Mateos, Jaime
Garcia Borràs, Marc
Osuna Oliveras, Sílvia
Filippone, Salvatore
Herranz, María Ángeles
Murata, Yasujiro
Solà i Puig, Miquel
Martín, Nazario
Abstract: The stereochemical outcome of cis-trans isomerization of optically pure [60], [70], and endohedral H2O@C60 fulleropyrrolidines reveals that the electronic nature of substituents, fullerene size, and surprisingly the incarcerated water molecule plays a crucial role in this rearrangement process. Theoretical DFT calculations are in very good agreement with the experimental fi ndings. On the basis of the experimental results and computational calculations, a plausible reaction mechanism involving the hydrogen-bonding assistance of the inner water molecule in the carbanion stabilization of endofullerene is proposed
Financial support by the European Research Council (ERC-320441-Chirallcarbon and FP7-PEOPLE-2013-CIG-630978 to S.O.), the Ministerio de Economia y Competitividad (MINECO) of Spain (projects CTQ2011-24652/BQU and CTQ2011-23156/BQU, JdlC contract to S.O, and AP2010-2517 to M.G.-B.), the CAM (PHOTOCARBON project S2013/MIT-2841), the Generalitat de Catalunya (project number 2014SGR931 and ICREA Academia 2009 to M.S.) is acknowledged. N.M. thanks to the Alexander von Humboldt Foundation
Format: application/pdf
Document access: http://hdl.handle.net/10256/10358
Language: eng
Publisher: American Chemical Society (ACS)
Collection: info:eu-repo/semantics/altIdentifier/doi/10.1021/ja5108854
info:eu-repo/semantics/altIdentifier/issn/0002-7863
info:eu-repo/semantics/altIdentifier/eissn/1520-5126
info:eu-repo/grantAgreement/MICINN//CTQ2011-23156/ES/AVANCES EN CATALISIS Y AROMATICIDAD/
AGAUR/2014-2016/2014 SGR-931
info:eu-repo/grantAgreement/EC/FP7/630978/EU/Computational Exploration of Directed Evolution rules for tuning enzymatic activities/DIREVENZYME
info:eu-repo/grantAgreement/EC/FP7/320441/EU/Chiral Allotropes of Carbon/CHIRALLCARBON
Rights: Tots els drets reservats
Subject: Ful·lerens
Fullerenes
Isomerització
Isomerization
Title: Enantiospecific cis-trans isomerization in chiral fulleropyrrolidines: Hydrogen-bonding assistance in the carbanion stabilization in H2O@C60
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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