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Bingel–Hirsch Addition of Diethyl Bromomalonate to Ion‐Encapsulated Fullerenes M@C 60 (M=Ø, Li + , Na + , K + , Mg 2+ , Ca 2+ , and Cl − )
Author(s) -
BesalúSala Pau,
Luis Josep M.,
Solà Miquel
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202003208
Subject(s) - fullerene , fullerene chemistry , reactivity (psychology) , ion , metal , chemistry , kinetics , chemical kinetics , inorganic chemistry , computational chemistry , organic chemistry , physics , medicine , alternative medicine , pathology , quantum mechanics
Abstract In the last 30 years, fullerene‐based materials have become popular building blocks for devices with a broad range of applications. Among fullerene derivatives, endohedral metallofullerenes (EMFs, M@C x ) have been widely studied owing to their unique properties and reactivity. For real applications, fullerenes and EMFs must be exohedrally functionalized. It has been shown that encapsulated metal cations facilitate the Diels–Alder reaction in fullerenes. Herein, the Bingel–Hirsch (BH) addition of ethyl bromomalonate over a series of ion‐encapsulated M@C 60 (M=Ø, Li + , Na + , K + , Mg 2+ , Ca 2+ , and Cl − ; Ø@C 60 stands for C 60 without any endohedral metal) is quantum mechanically explored to analyze the effect of these ions on the BH addition. The results show that the incarcerated ion has a very important effect on the kinetics and thermodynamics of this reaction. Among the systems studied, K + @C 60 is the one that leads to the fastest BH reaction, whereas the slowest reaction is given by Cl − @C 60 .