Counter anion in Li⁺‐encapsulated C₆₀ can further enhance the rate of Diels–Alder reaction: A DFT study

Abstract

Density functional theory calculations were carried out to investigate the Diels–Alder cycloaddition between cyclopentadiene and C60 after the encapsulation of Li+ ion with transition states identified and confirmed by intrinsic reaction coordinate calculations. Our results showed that the Li+‐encapsulation results in a lower energy barrier and the presence of counter anion PF6− can further reduce the energy barrier, making the trend in agreement with the experimental results. In addition, the influencing factors on the reactivity of Li+‐encapsulated fullerenes such as counter anion and the position of Li+ in C60 were discussed. This study aims to provide a better understanding of Diels–Alder reaction with Endohedral Metallofullerenes to allow more efficient functionalization of fullerenes.

A Theoretical Study on the Stability of PtL2 Complexes of Endohedral Fullerenes: The Influence of Encapsulated Ions, Cage Sizes, and Ligands

“…From then on, various kinds of FTMC have been prepared and structurally characterized. , An interesting characteristic for such an FTMC is that it can encage atoms, ions, and small molecules to form endohedral complexes, which is named endohedral metallofullerenes, because the metal atoms are encapsulated within a hollow carbon cage. Since then, many other experimental and computational works in such fields concerning cation-/anion-encapsulated fullerene chemistry have been greatly achieved. − Recently, Tobita and co-workers reported the preparations and structural characterizations of the intriguing FTMC, that is, iridium and platinum complexes of the lithium-cation-encapsulated fullerene Li + @C 60 …”

Computational insights into themulti‐Diels–Alderreactions of neutralC60and its Li+encapsulated analogue: A density functional theory study

“…Zhang et al [43] investigated the effect of counter anion in Li + -encapsulated C 60 during the DA reaction. Cui et al [44] showed the thermodynamic feasibility of cycloaddition reactions between CpH and Ca 2+ @C 60 as well as M + @C 60 (M = Li, Na, K, Rb, and Cs).…”