Electronic Structure Contributions of Non-Heme Oxo-Iron(V) Complexes to the Reactivity

Oxo-iron(V) species have been implicated in the catalytic cycle of the Rieske dioxygenase. Their synthetic analog, [Fe^V(O)(OC(O)CH₃)(PyNMe₃)]²⁺ (1, PyNMe₃ = 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene-3,6,9-trimethyl), derived from the O-O bond cleavage of its acetylperoxo iron(III) precursor, has been shown experimentally to perform regio- and stereoselective C-H and C═C bond functionalization. However, its structure-activity relation is poorly understood. Herein we present a detailed electronic-structure and spectroscopic analysis of complex 1 along with well-characterized oxo-iron(V) complexes, [Fe^V(O)(TAML)]^- (2, TAML = tetraamido macrocyclic ligand), [Fe^V(O)(TMC)(NC(O)CH₃)]⁺ (4, TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), and [Fe^V(O)(TMC)(NC(OH)CH₃)]²⁺ (4-H⁺), using wave function-based multireference complete active-space self-consistent field calculations. Our results reveal that the x/ y anisotropy of the ⁵⁷Fe A-matrix is not a reliable spectroscopic marker to identify oxo-iron(V) species and that the drastically different A _x and A _y values determined for complexes 1, 4, and 4-H⁺ have distinctive origins compared to complex 2, a genuine oxo-iron(V) species. Complex 1, in fact, has a dominant character of [Fe^IV(O···OC(O)CH₃)^2-•]²⁺, i.e., an S_Fe = 1 iron(IV) center antiferromagnetically coupled to an O-O σ* radical, where the O-O bond has not been completely broken. Complex 4 is best described as a triplet ferryl unit that strongly interacts with the trans acetylimidyl radical in an antiferromagnetic fashion, [Fe^IV(O)(^•N═C(O^-)CH₃)]⁺. Complex 4-H⁺ features a similar electronic structure, [Fe^IV(O)(^•N═C(OH)CH₃)]²⁺. Owing to the remaining approximate half σ-bond in the O-O moiety, complex 1 can arrange two electron-accepting orbitals (α σ*_O-O and β Fe-d _xz) in such a way that both orbitals can simultaneously interact with the doubly occupied electron-donating orbitals (σ_C-H or π_C-C). Hence, complex 1 can promote a concerted yet asynchronous two-electron oxidation of the C-H and C═C bonds, which nicely explains the stereospecificity observed for complex 1 and the related species.