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A series of iron(IV) oxo complexes, which differ in the donor (CH 2 py or CH 2 COO - ) cis o 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 ν Fe═O values of 832 ± 2 cm -1 indicate similar Fe IV ═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 ( k  H  /k  D = 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, [Fe IV O(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.

inorganic chemistry

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

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