Understanding the Reactivity of Ion-Encapsulated Fullerenes.

Authors :: García-Rodeja Y
Solà M
Bickelhaupt FM
Fernández I
Source :: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2017 Aug 16; Vol. 23 (46), pp. 11030-11036. Date of Electronic Publication: 2017 Jul 04.
Publication Year :: 2017
Abstract: The influence of the encapsulation of an ion inside the C <subscript>60</subscript> fullerene cage on its exohedral reactivity was explored by means of DFT calculations. To this end, the Diels-Alder reaction between 1,3-cyclohexadiene and M@C <subscript>60</subscript> (M=Li <superscript>+</superscript> , Na <superscript>+</superscript> , K <superscript>+</superscript> , Be <superscript>2+</superscript> , Mg <superscript>2+</superscript> , Al <superscript>3+</superscript> , and Cl <superscript>-</superscript> ) was studied and compared to the analogous process involving the parent C <subscript>60</subscript> fullerene. A significant enhancement of the Diels-Alder reactivity is found for systems having an endohedral cation, whereas a clear decrease in reactivity is observed when an anion is encapsulated in the C <subscript>60</subscript> cage. The origins of this reactivity trend were quantitatively analyzed in detail by using the activation strain model of reactivity in combination with energy decomposition analysis.<br /> (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)