Influence of the charge on the reactivity of azafullerenes

Abstract

The influence of the charge on the Diels–Alder reactivity of azafullerenes (C59N+ and C59N−) has been computationally explored by means of density functional theory calculations.

Understanding chemical reactivity using the activation strain model

“…The ASM can be applied to all unimolecular and bimolecular reactions in both homogeneous and heterogeneous systems and has been used routinely by theoretical and experimental chemists [28][29][30][31][32][33][34][35][36][37][38][39][40][41][42] . We provide specific examples of the ASM being applied to understand inorganic, organic, and supramolecular chemistries, namely, the transition metal-mediated oxidative addition of C-X bonds in cross-coupling reactions, the reactivity of cycloalkynes in 1,3-dipolar cycloadditions, the reactivity of dihalogen-catalyzed Michael addition reactions, and the bonding mechanism in hydrogen-bonded systems.…”

PyFrag 2019—Automating the exploration and analysis of reaction mechanisms

“…For instance, we have previously used the ASM to understand how the reaction barrier varies when different bonds are activated by palladium, or how ligands can change the activating capability of palladium, or how and why other metal centers perform differently in cross‐coupling reactions compared to palladium . In addition, the ASM has been successfully applied to understand the quantitative factors governing molecular reactivity in other systems like cycloadditions, metalorganic catalysis, and substitution reactions …”

Understanding the reactivity of polycyclic aromatic hydrocarbons and related compounds

“…60,61 Based on the computed barriers, the following Diels-Alder reactivity trend was found: C 59 N + > C 60 > C 59 NH > C 59 N À . 62 Once again, the interaction energy between the reactants was found to be the key factor governing the reactivity of these azafullerenes. Despite that, the weaker DE int computed for C 59 NH or C 59 N À does not derive from weaker orbital interactions but from a more destabilizing Pauli repulsion between closed-shells as a consequence of the presence of two additional p-electrons in these systems compared to C 59 N + or C 60 .…”

“…Despite that, the weaker DE int computed for C 59 NH or C 59 N À does not derive from weaker orbital interactions but from a more destabilizing Pauli repulsion between closed-shells as a consequence of the presence of two additional p-electrons in these systems compared to C 59 N + or C 60 . 62 The modication of the electronic structure and reactivity of PAHs is not restricted to the incorporation of group 13-16 heteroatoms. In fact, it can also be achieved by incorporating transition metal fragments in their structures instead.…”