The new ligand L(1), 1-N,1-N-bis(pyridine-2-ylmethyl)-3-N-(pyridine-2-ylmethylidene)benzene-1,3-diamine, was synthesized as a platform for the study of bimetallic complexes containing redox-active ligands. The asymmetric L(1) contains a redox-active α-iminopyridine unit bridged to redox-inert bis(2-pyridylmethyl)amino counterpart and offers two distinct coordination sites. The coordination chemistry of L(1) with Fe, Cu, and Zn was examined. Reaction with zinc afforded the asymmetric binuclear complex [(L(1))Zn(2)Cl(4)] (1), whereas the symmetric [(L(1))(2)Fe(2)(OTf)(2)](OTf)(2) (2) and [(L(1))(2)Cu(2)](OTf)(4) (3) were isolated in reactions with iron and copper. Both metal- and ligand-centered redox processes are available to the series of metal compounds. EPR and Mössbauer spectroscopy and magnetic susceptibility studies establish that both 2 and 3 are paramagnetic; the vanishingly small ferromagnetic interaction produces decoupled high-spin Fe(II) (S = 2) ions in 2. DFT calculations provide further insight into the nature of the exchange interactions in the dimeric systems.

C−H oxidation is catalyzed by a high‐spin ferrous dimer, [(L1)2Fe2(CH3CN)2](PF6)4 (1), that offers two identical functional sites, separated by > 7 Å. The complex provides a unique contrast to both mononuclear and binuclear non‐heme enzyme active sites as well as biomimetic complexes. The oxidative activity of 1 was examined using a range of substrates (cyclohexene, 9,10‐dihydroanthracene, xanthene, triphenylmethane, triphenylphosphine, and cyclohexane) and PhIO as an oxidant. The studies establish the O‐atom transfer and H‐atom abstraction ability of the diiron complex. We further probe the energetics of cyclohexene oxidation by 1 and derive putative mechanisms for the pathways of allylic alcohol and epoxide formation using density functional theory (DFT) calculations. The DFT calculations indicate that the oxidation reactions proceed via a FeIV=O species in the triplet state, and that both iron centers can act independently of each other. The combined results provide insight into hydrocarbon oxidation by non‐coupled binuclear systems.