High-valent Fe(IV)-oxo species have been found to be key oxidizing intermediates in the mechanisms of mononuclear iron heme and non-heme enzymes. Synthetic non-heme Fe(IV)-oxo molecular complexes have been successfully synthesized and characterized, but their catalytic reactivity is typical lower than the enzymatic analogues. One of the reasons of their lower reactivity is the self-oxidation mechanism that undergo due to the close proximity of ligand’s methyl groups to the active site. We have performed high-level wave function theory calculations in a series of non-heme Fe(IV)-oxo model complexes in order to elucidate the electronic properties and the ligand field effects on the substrate oxidation and self-oxidation reactions. Geometrical and electronic structure properties such as the accessibility of the Fe(III)-oxyl reactive channels are compared to C-H reaction barriers and correlated with their catalytic performance. The transferability of our conclusions from the comparable study is tested on well-studied non-heme Fe(IV)-oxo complexes, such as the [FeIV(O)(TMG3tren)]2+, and strategies that enhance the catalytic activity will be provided.

Understanding the electronic effects that control the non-heme Fe(IV)-oxo reaction channels for C-H activation

255th National Meeting (2018)

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