Inorganic Chemistry
Inorganic Chemistry
5 years ago

Characterization of the Fleeting Hydroxoiron(III) Complex of the Pentadentate TMC-py Ligand

Characterization of the Fleeting Hydroxoiron(III) Complex of the Pentadentate TMC-py Ligand
Gerald Knizia, Johannes E. M. N. Klein, Lawrence Que, Ang Zhou, Yisong Guo, Christopher J. Cramer, Ruixi Fan, Wei-Min Ching
To model fleeting hydroxoiron(III) intermediates formed in the reactions of biological oxoiron(IV) oxidants with C−H bonds, we trapped a mononuclear high-spin hydroxoiron(III) complex, [FeIII(OH)(TMC-py)]2+ (3), in ∼80% yield from the reaction of [FeIV(O)(TMC-py)]2+ with 1,4-cyclohexadiene at −40 °C. Complex 3 has an intense near-UV band at 335 nm and a 1.84 Å Fe−OH bond. It readily oxidizes TEMPOH at −40 °C by a reaction classified by DFT as a proton-coupled electron transfer.

Publisher URL: http://dx.doi.org/10.1021/acs.inorgchem.7b01459

DOI: 10.1021/acs.inorgchem.7b01459

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