Oxoiron(IV) species are invoked as key intermediates in the catalytic cycles of many non-heme oxygen-activating enzymes. Synthetic chemists have modeled these species with over 70 oxoiron(IV) complexes over the last decade. This study focuses on an oxoiron(IV) complex supported by the pentadentate ligand BnTPEN (N'-benzyl-N',N'',N''-tris(pyridin-2-ylmethyl)ethane-1,2-diamine), which is one of the most reactive complexes found to oxidize cyclohexane. Our goal is to further increase its C–H bond cleaving reactivity by introducing alpha-substituents on the pyridine donors, which we expect will result in weakening the ligand field of this oxoiron(IV) unit, thereby decreasing its thermal stability and increasing the rates of C—H bond cleavage. Non-heme oxoiron(IV) intermediates are invoked in enzymatic cycles of many oxygen activating enzymes. Synthetic chemists have attempted to model these short-lived intermediates using many complexes. Four of these complexes supported by pentadentate ligands have been crystallographically characterized. They all possess some form of a pseudo-mirror plane symmetry. This work presents the crystal structure of an oxoiron(IV) complex supported by a pentadentate ligand BnTPEN (N'-benzyl-N',N'',N''-tris(pyridin-2-ylmethyl)ethane-1,2-diamine) that does not possess Cs symmetry and is capable of breaking the strong C—H bonds of cyclohexane. The properties of this complex in solvents other than the standard acetonitrile solvent are also explored in this work.

Tuning the C—H bond cleavage ability of an oxoiron(IV) complex structural properties of an oxoiron(IV) complex supported by a pentadentate ligand

253rd National Meeting (2017)

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