DUGi

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

http://dugi.udg.edu/item/http:@@@@hdl.handle.net@@2072@@295642

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)