Ethane C-H bond activation on the Fe(iv)-oxo species in a Zn-based cluster of metal-organic frameworks: a density...

We first investigate the feasibility of designing a Fe-oxo complex for the activation of alkane C-H bonds by (a) incorporating an Fe ion into a Zn-based cluster derived from a metal-organic framework (MOF) and (b) creating the Fe-oxo complex via decomposition of N₂O over a Fe²⁺-substituted Zn-based cluster (Fe-Zn₃O(pyrazole)₆). From the energy profile, it turns out that both steps should be feasible and that the resulting Fe-oxo complex is stable. In the main step, we then investigate the reactivity of this Fe-oxo cluster for the C-H bond cleavage of ethane by calculating the reaction energy profile and analyzing the electronic structure along the relevant steps. Two mechanisms, namely the σ and π pathways on the triplet and quintet potential energy surfaces, were unraveled for this study of catalytic activity. It is shown that the σ pathway on the quintet surface is kinetically and thermodynamically favorable with an energy barrier of 22.5 kcal mol^-1. The π pathway on the quintet and triplet surfaces has activation energies of 26.9 kcal mol^-1 and 24.9 kcal mol^-1, respectively. An alternative unusual pathway called the δ mechanism on the triplet surface is also observed with an energy barrier of 12.6 kcal mol^-1. It is, however, thermodynamically at a disadvantage compared to the σ pathway on the quintet surface. Favorable d-d interaction on the Fe center and less steric hindrance from the equatorial ligands at the transition state are the key factors that cause the σ pathway on the quintet surface to have the lowest activation energy. All our calculations are of the cluster type and have been performed at the B3LYP-D3/def2-TZVP level of theory.