Pathways of the Extremely Reactive Iron(IV)-oxido complexes with Tetradentate Bispidine Ligands.

ABSTRACT: The nonheme iron(IV)-oxido complex trans-N3-[(L¹ )Fe^IV =O(Cl)]⁺ , where L¹ is a derivative of the tetradentate bispidine 2,4-di(pyridine-2-yl)-3,7-diazabicyclo[3.3.1]nonane-1-one, is known to have an S=1 electronic ground state and to be an extremely reactive oxidant for oxygen atom transfer (OAT) and hydrogen atom abstraction (HAA) processes. Here we show that, in spite of this ferryl oxidant having the "wrong" spin ground state, it is the most reactive nonheme iron model system known so far and of a similar order of reactivity as nonheme iron enzymes (C-H abstraction of cyclohexane, -90 °C (propionitrile), t_1/2 =3.5 sec). Discussed are spectroscopic and kinetic data, supported by a DFT-based theoretical analysis, which indicate that

SUBMITTER: Abu-Odeh M 

PROVIDER: S-EPMC8456976 | biostudies-literature | 2021 Aug

REPOSITORIES: biostudies-literature