Theoretical Identification of the Factors Governing the Reactivity of C-H Bond Activation by Non-Heme Iron(IV)-Oxo Complexes.

Selective functionalization of C-H bonds provides a straightforward approach to a large variety of well-defined derivatives. High-valent mononuclear iron(IV)-oxo complexes are proposed to carry out these C-H activation reactions in enzymes or in biomimetic syntheses. In this Minireview, we aim to highlight the features that delineate the distinct reactivity of non-heme oxo-iron(IV) motifs to cleave strong C-H bonds in hydrocarbons, primarily focusing on the hydrogen atom transfer (HAT) process. We describe how the structural and electronic properties of supporting ligands modulate the oxidative property of the iron(IV)-oxo complexes. Furthermore, we highlight the decisive role played by spin-state in these biomimetic reactions. We also discuss how tunneling and external perturbations like electric field influence the transfer of hydrogen atoms. Lastly, we emphasize how computations could work as a practical guide to sketch and develop synthetic models with greater efficacy.