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The Regioselectivity of Bingel-Hirsch Cycloadditions on Isolated Pentagon Rule Endohedral Metallofullerenes

In this work, the Bingel-Hirsch addition of diethylbromomalonate to all non-equivalent bonds of Sc3N@D3h-C78 was studied using density functional theory calculations. The regioselectivities observed computationally allowed the proposal of a set of rules, the predictive aromaticity criteria (PAC), to identify the most reactive bonds of a given endohedral metallofullerene based on a simple evaluation of the cage structure. The predictions based on the PAC are fully confirmed by both the computational and experimental exploration of the Bingel-Hirsch reaction of Sc3N@D5h-C80, thus indicating that these rules are rather general and applicable to other isolated pentagon rule endohedral metallofullerenes

Aquest mateix article està publicat a l’edició alemanya d’’Angewandte Chemie’ (ISSN 0044-8249, EISSN 1521-3757), 2016, vol. 128, núm. 7, p. 2420-2423. DOI http://dx.doi.org/10.1002/ange.201509057

We are grateful to the Spanish MINECO (CTQ2014-54306-P, CTQ2014-52525-P, CTQ2014-59212-P, and JdlC contract to S.O.), the Catalan DIUE (2014SGR931, ICREA Academia 2014 Award to M.S. and XRQTC), and the FEDER fund (UNGI10-4E-801) for financial support. M.G.-B. thanks the Spanish MECD for a PhD grant (AP2010-2517) and S.O. the European Commission for CIG project (FP7-PEOPLE-2013- CIG-630978). CESCA and BSC-CNS are acknowledged. M.R.C, M.I. and L.E. thanks the NSF for generous support of this work under grant (CHE-1408865) and to the NSFPREM program (DMR-1205302). The Robert A. Welch Foundation is also gratefully acknowledged for an endowed chair to L.E. (grant AH-0033)

© Angewandte Chemie International Edition, 2016, vol. 55, núm. 7, p. 2374-2377

Wiley-VCH Verlag

Author: Garcia Borràs, Marc
Cerón, Maira R.
Osuna Oliveras, Sílvia
Izquierdo, Marta
Luis Luis, Josep Maria
Echegoyen, Luis A.
Solà i Puig, Miquel
Date: 2016
Abstract: In this work, the Bingel-Hirsch addition of diethylbromomalonate to all non-equivalent bonds of Sc3N@D3h-C78 was studied using density functional theory calculations. The regioselectivities observed computationally allowed the proposal of a set of rules, the predictive aromaticity criteria (PAC), to identify the most reactive bonds of a given endohedral metallofullerene based on a simple evaluation of the cage structure. The predictions based on the PAC are fully confirmed by both the computational and experimental exploration of the Bingel-Hirsch reaction of Sc3N@D5h-C80, thus indicating that these rules are rather general and applicable to other isolated pentagon rule endohedral metallofullerenes
Aquest mateix article està publicat a l’edició alemanya d’’Angewandte Chemie’ (ISSN 0044-8249, EISSN 1521-3757), 2016, vol. 128, núm. 7, p. 2420-2423. DOI http://dx.doi.org/10.1002/ange.201509057
We are grateful to the Spanish MINECO (CTQ2014-54306-P, CTQ2014-52525-P, CTQ2014-59212-P, and JdlC contract to S.O.), the Catalan DIUE (2014SGR931, ICREA Academia 2014 Award to M.S. and XRQTC), and the FEDER fund (UNGI10-4E-801) for financial support. M.G.-B. thanks the Spanish MECD for a PhD grant (AP2010-2517) and S.O. the European Commission for CIG project (FP7-PEOPLE-2013- CIG-630978). CESCA and BSC-CNS are acknowledged. M.R.C, M.I. and L.E. thanks the NSF for generous support of this work under grant (CHE-1408865) and to the NSFPREM program (DMR-1205302). The Robert A. Welch Foundation is also gratefully acknowledged for an endowed chair to L.E. (grant AH-0033)
Format: application/pdf
ISSN: 1433-7851 (versió paper)
1521-3773 (versió electrònica)
Document access: http://hdl.handle.net/10256/12194
Language: eng
Publisher: Wiley-VCH Verlag
Collection: MINECO/PE 2015-2017/CTQ2014-54306-P
MINECO/PE 2015-2017/CTQ2014-59212-P
AGAUR/2014-2016/2014 SGR-931
Versió postprint del document publicat a: http://dx.doi.org/10.1002/anie.201509057
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/630978
Is part of: © Angewandte Chemie International Edition, 2016, vol. 55, núm. 7, p. 2374-2377
Rights: Tots els drets reservats
Subject: Aromaticitat (Química)
Aromaticity (Chemistry)
Fullerenes
Ful·lerens
Funcional de densitat, Teoria del
Density functionals
Química supramolecular
Supramolecular chemistry
Bingel-Hirsch, Reacció de
Bingel-Hirsch reaction
Ciclització (Química)
Ring formation (Chemistry)
Title: The Regioselectivity of Bingel-Hirsch Cycloadditions on Isolated Pentagon Rule Endohedral Metallofullerenes
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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