American Chemical Society
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Engineering the Oxidative Potency of Non-Heme Iron(IV) Oxo Complexes in Water for C–H Oxidation by a cis Donor and Variation of the Second Coordination Sphere

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journal contribution
posted on 2021-01-20, 15:19 authored by Christina Wegeberg, Mathias L. Skavenborg, Andrea Liberato, James N. McPherson, Wesley R. Browne, Erik D. Hedegård, Christine J. McKenzie
A series of iron­(IV) oxo complexes, which differ in the donor (CH2py or CH2COO) cis to the oxo group, three with hemilabile pendant donor/second coordination sphere base/acid arms (pyH/py or ROH), have been prepared in water at pH 2 and 7. The νFeO values of 832 ± 2 cm–1 indicate similar FeIVO bond strengths; however, different reactivities toward C–H substrates in water are observed. HAT occurs at rates that differ by 1 order of magnitude with nonclassical KIEs (kH/kD = 30–66) consistent with hydrogen atom tunneling. Higher KIEs correlate with faster reaction rates as well as a greater thermodynamic stability of the iron­(III) resting states. A doubling in rate from pH 7 to pH 2 for substrate C–H oxidation by the most potent complex, that with a cis-carboxylate donor, [FeIVO­(Htpena)]2+, is observed. Supramolecular assistance by the first and second coordination spheres in activating the substrate is proposed. The lifetime of this complex in the absence of a C–H substrate is the shortest (at pH 2, 3 h vs up to 1.3 days for the most stable complex), implying that slow water oxidation is a competing background reaction. The iron­(IV)O complex bearing an alcohol moiety in the second coordination sphere displays significantly shorter lifetimes due to a competing selective intramolecular oxidation of the ligand.