title: Ethane C-H bond activation on the Fe(iv)-oxo species in a Zn-based cluster of metal-organic frameworks: a density functional theory study.
abstract: 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-1and 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.
authors.affiliation: Department of Chemical and Biomolecular Engineering, School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong 21210, Thailand. sareeya.b@vistec.ac.th.
authors.forename: Sarawoot
authors.identifier: http://orcid.org/0000-0001-6693-1244
authors.initials: S
authors.lastname: Impeng
authors.affiliation: Department of Chemical and Biomolecular Engineering, School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong 21210, Thailand. sareeya.b@vistec.ac.th.
authors.forename: Siwarut
authors.initials: S
authors.lastname: Siwaipram
authors.affiliation: Department of Chemical and Biomolecular Engineering, School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong 21210, Thailand. sareeya.b@vistec.ac.th.
authors.forename: Sareeya
authors.initials: S
authors.lastname: Bureekaew
authors.affiliation: Institute of Ion Physics and Applied Physics, University of Innsbruck, 6020 Innsbruck, Austria.
authors.forename: Michael
authors.initials: M
authors.lastname: Probst