Details

Autor(en) / Beteiligte

• Zhang, Dawei
• Li, Haisheng
• Wang, Huixian
• Li, Liben

Titel

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

Ist Teil von

• International journal of quantum chemistry, 2016-12, Vol.116 (24), p.1846-1850

Ort / Verlag

Hoboken: Blackwell Publishing Ltd

Erscheinungsjahr

2016

Quelle

Wiley-Blackwell Full Collection

Beschreibungen/Notizen

• 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. While encapsulated metal ions are known to affect the rate of Diels–Alder reactions catalyzed by fullerenes, counter anions are not considered to be a significant factor in the reaction. First‐principles calculations reveal that the counter anion selection, for example, PF6− in this study, can further enhance the rate of Diels–Alder reaction by attracting the encapsulated cation to a position closer to fullerene surface and thus facilitating more charge transfer.