Understanding the Reactivity of Fullerenes Through the Activation Strain Model

Abstract

The Activation Strain Model of reactivity nowadays constitutes a powerful tool to aid quantitative understanding of chemical reactions, and also their design. This approach, combined with the Energy Decomposition Analysis method, has been really helpful for our current understanding of different fundamental transformations in chemistry. This Microreview illustrates the usefulness of this methodology in providing more insight into the chemistry of fullerenes. To this end, representative recent applications, ranging from the regioselectivity in Diels–Alder cycloaddition to the reactivity of endohedral fullerenes, are presented.

Influence of the Lewis Acid/Base Pairs on the Reactivity of Geminal E‐CH2‐E′ Frustrated Lewis Pairs

“…This behavior has also been observed not only in our previousw ork focusedo nt he strongly relatedH 2 activation mediated by geminal B/N FLPs, [13] but also in completely different processes, such as pericyclic reactions. [29] Interestingly,t he interaction energy between the deformed reactants (DE int ), which is rather similar fora ll systems along the entire reactionc oordinate, only becomes significantly different at the corresponding transition states where it increases (i.e.,b ecomesm ore stabilizing) in the order E = N < P < Sb. This is exactly the opposite trend to the activation barriers,w hich strongly suggestst hat the observed reactivity trend is not related to the interaction between the reactants.…”

autoDIAS: a python tool for an automated distortion/interaction activation strain analysis

“…This analysis can be applied to single geometries or multiple geometries along a scan or reaction coordinate, to provide information on the nature of interaction between the fragments and the potential energy surface. This method has been widely applied for a broad range of chemical systems such as cycloadditions, ene reactions, metal complexes and catalysis, organocatalysis, and addition and substitution reactions …”

“…This analysis can be applied to single geometries or multiple geometries along a scan or reaction coordinate, to provide information on the nature of interaction between the fragments and the potential energy surface. This method has been widely applied for a broad range of chemical systems such as cycloadditions, [6][7][8][9][10][11][12][13][14][15][16][17][18] ene reactions, [19] metal complexes and catalysis, [20][21][22][23][24][25][26][27] organocatalysis, [28][29][30][31] and addition [32] and substitution reactions. [33][34][35] The implementation of a DIAS analysis is straight forward and can be performed using any electronic structure software.…”

Path-dependency of energy decomposition analysis & the elusive nature of bonding

“…ΔVelstat and ΔEoi are associated with covalent and ionic contributions to the bonding, respectively. [5][6][7]22,23 Finally, if the density functional used in the calculations contains dispersion corrections (not in our case), then in Eq. ( 2) there is another term, Edisp, that takes into account the interactions due to dispersion forces.…”