Soluble methane monooxygenase (sMMO) carries out methane hydroxylation in a catalytic cycle involving the formation of a peroxodiiron(III) intermediate P by the reaction of the diiron(II) enzyme with O2 and its subsequent conversion to intermediate Q, the diiron(IV) oxidant that hydroxylates methane. Synthetic diiron(IV) complexes that can serve as models for Q are rare, particularly those generated by a reaction sequence analogous to that of sMMO. In this poster, we show that [FeII(Me3NTB)(CH3CN)](OTf)2 (Me3NTB = tris((1-methyl-1H-benzo[d]imidazol-2-yl)methyl)amine) reacts with O2 in the presence of base to generate a (μ-1,2- peroxo)diiron(III) adduct that in turn undergoes O−O bond cleavage upon treatment with the Lewis acid Sc3+ to convert into a bis(μ-oxo)diiron(IV) complex. This sequence of reactions provides a synthetic precedent for the analogous conversion of P to Q in the catalytic cycle of sMMO.

Twists and turns in making a functional model for activating O2 at active sites of nonheme diiron monooxygenases

ACS Spring 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.