Photoinduced O₂‑Dependent Stepwise Oxidative Deglycination of a Nonheme Iron(III) Complex

The iron­(III) complex [Fe­(tpena)]2+ (tpena = N,N,N′-tris­(2-pyridylmethyl)­ethylendiamine-N′-acetate) undergoes irreversible O2-dependent N-demethylcarboxylation to afford [FeII(SBPy3)­(MeCN)]2+ (SBPy3 = N,N-bis­(2-pyridylmethyl)­amine-N-ethyl-2-pyridine-2-aldimine), when irradiated with near-UV light. The loss of a mass equivalent to the glycyl group in a process involving consecutive C–C and C–N cleavages is documented by the measurement of the sequential production of CO2 and formaldehyde, respectively. Time-resolved UV–vis absorption, Mössbauer, EPR, and Raman spectroscopy have allowed the spectroscopic characterization of two iron-based intermediates along the pathway. The first of these, proposed to be a low-spin iron­(II)-radical ligand complex, reacts with O2 in the rate-determining step to produce a putative alkylperoxide complex. DFT calculations suggest that this evolves into an Fe­(IV)-oxo species, which can abstract a hydrogen atom from a cis methylene group of the ligand to give the second spectroscopically identified intermediate, a high-spin iron­(III)-hydroxide of the product oxidized ligand, [FeIII(OH)­(SBPy3)]2+. Reduction and exchange of the cohydroxo/water ligand produces the crystallographically characterized products [FeII(SBPy3)­(X)]2+/3+, X = MeCN, [Zn­(tpena)]+.