Diels-Alder cycloaddition of cyclopentadiene to C60 and Si60 and their endohedral Li+ counterparts
Both silicon and carbon are elements located in the group 14 on the periodic table. Despite some similarities between these two elements, differences in reactivity are important, and whereas carbon is a central element in all known forms of life, silicon is barely found in biological systems. Here,...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2025 |
| País: | España |
| Institución: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:10256/26547 |
| Acceso en línea: | http://hdl.handle.net/10256/26547 |
| Access Level: | acceso abierto |
| Palabra clave: | Ciclització (Química) Ring formation (Chemistry) Diels-Alder, Reacció de Diels-Alder reaction |
| Sumario: | Both silicon and carbon are elements located in the group 14 on the periodic table. Despite some similarities between these two elements, differences in reactivity are important, and whereas carbon is a central element in all known forms of life, silicon is barely found in biological systems. Here, we investigate the Diels-Alder cycloaddition reaction of cyclopentadiene (CP) and cyclopentasildiene (CPSi) with fullerenes C60, Li+@C60, Si60, and Li+@Si60 using Density Functional Theory (DFT) methods. The results reveal distinct kinetic and thermodynamic trends that govern reactivity and selectivity. For C60, the [6,6] pathway is kinetically and thermodynamically favored, whereas for Si60, the [5,6] pathway is preferred thermodynamically but not kinetically. Introduction of lithium cations increases the reactivity of both C60 and Si60. Energy decomposition analysis unveils the importance of the components of the interaction energy between the CPSi and the corresponding fullerenes. The findings provide insights into the interplay of electronic structure, substrate reactivity, and fullerene electrophilicity in cycloaddition reactions |
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