10-Fold Increase in Hydrogen Atom Transfer Reactivity for a Series of <i>S</i> = 1 Fe^IV═O Complexes Over the <i>S</i> = 2 [(TQA)Fe^IV═O]²⁺ Complex via Entropic Lowering of Reaction Barriers by Secondary Sphere Cycloalk

Nonheme iron enzymes utilize <i>S</i> = 2 iron(IV)-oxo intermediates as oxidants in biological oxygenations. In contrast, corresponding synthetic nonheme Fe^IV═O complexes characterized to date favor the <i>S</i> = 1 ground state that generally shows much poorer oxidative reactivity than their <i>S</i> = 2 counterparts. However, one intriguing exception found by Nam a decade ago is the <i>S</i> = 1 [Fe^IV(O)(Me₃NTB)]²⁺ complex (Me₃NTB = [tris((<i>N</i>-methyl-benzimidazol-2-yl)methyl)amine], <b>1O</b>) with a hydrogen atom transfer (HAT) reactivity that is 70% that of the <i>S</i> = 2 [Fe^IV(O)(TQA)]²⁺ complex (TQA = tris(2-quinolylmethyl)amine, <b>3O</b>). In our efforts to further explore this direction, we have unexpectedly uncovered a family of new <i>S</i> = 1 complexes with HAT reaction rates beyond the currently reported limits in the tripodal ligand family, surpassing oxidation rates found for the <i>S</i> = 2 [Fe^IV(O)(TQA)]²⁺ complex by as much as an order of magnitude. This is achieved simply by replacing the secondary sphere methyl groups of the Me₃NTB ligand with larger cycloalkyl-CH₂ (R groups in <b>2O</b>^<b>R</b>) moieties ranging from <i>c</i>-propylmethyl to <i>c</i>-hexylmethyl. These <b>2O</b>^<b>R</b> complexes show Mössbauer data at 4 K and ¹H NMR spectra at 193 and 233 K that reveal <i>S</i> = 1 ground states, in line with DFT calculations. Nevertheless, they give rise to the most reactive synthetic nonheme oxoiron(IV) complexes found to date within the tripodal ligand family. Our DFT study indicates transition state stabilization through entropy effects, similar to enzymatic catalysis.