Search

Formation of the O-O bond is considered the critical step in oxidative water cleavage to produce dioxygen. High-valent metal complexes with terminal oxo (oxido) ligands are commonly regarded as instrumental for oxygen evolution, but direct experimental evidence is lacking. Herein, we describe the formation of the O-O bond in solution, from non-heme, N5 -coordinate oxoiron(IV) species. Oxygen evolution from oxoiron(IV) is instantaneous once meta-chloroperbenzoic acid is administered in excess. Oxygen-isotope labeling reveals two sources of dioxygen, pointing to mechanistic branching between HAT (hydrogen atom transfer)-initiated free-radical pathways of the peroxides, which are typical of catalase-like reactivity, and iron-borne O-O coupling, which is unprecedented for non-heme/peroxide systems. Interpretation in terms of [FeIV (O)] and [FeV (O)] being the resting and active principles of the O-O coupling, respectively, concurs with fundamental mechanistic ideas of (electro-) chemical O-O coupling in water oxidation catalysis (WOC), indicating that central mechanistic motifs of WOC can be mimicked in a catalase/peroxidase setting.

Formation of the O−O bond is considered the critical step in oxidative water cleavage to produce dioxygen. High‐valent metal complexes with terminal oxo (oxido) ligands are commonly regarded as instrumental for oxygen evolution, but direct experimental evidence is lacking. Herein, we describe the formation of the O−O bond in solution, from non‐heme, N5‐coordinate oxoiron(IV) species. Oxygen evolution from oxoiron(IV) is instantaneous once meta‐chloroperbenzoic acid is administered in excess. Oxygen‐isotope labeling reveals two sources of dioxygen, pointing to mechanistic branching between HAT (hydrogen atom transfer)‐initiated free‐radical pathways of the peroxides, which are typical of catalase‐like reactivity, and iron‐borne O−O coupling, which is unprecedented for non‐heme/peroxide systems. Interpretation in terms of [FeIV(O)] and [FeV(O)] being the resting and active principles of the O−O coupling, respectively, concurs with fundamental mechanistic ideas of (electro‐) chemical O−O coupling in water oxidation catalysis (WOC), indicating that central mechanistic motifs of WOC can be mimicked in a catalase/peroxidase setting.

The ligand-field strength in metal complexes of polydentate ligands depends critically on how the ligand backbone places the donor atoms in three-dimensional space. Distortions from regular coordination geometries are often observed. In this work, we study the isolated effect of ligand-sphere distortion by means of two structurally related pentadentate ligands of identical donor set, in the solid state (X-ray diffraction, (57)Fe-Mössbauer spectroscopy), in solution (NMR spectroscopy, UV/Vis spectroscopy, conductometry), and with quantum-chemical methods. Crystal structures of hexacoordinate iron(II) and nickel(II) complexes derived from the cyclic ligand L(1) (6-methyl-6-(pyridin-2-yl)-1,4-bis(pyridin-2-ylmethyl)-1,4-diazepane) and its open-chain congener L(2) (N(1),N(3),2-trimethyl-2-(pyridine-2-yl)-N(1),N(3)-bis(pyridine-2-ylmethyl) propane-1,3-diamine) reveal distinctly different donor set distortions reflecting the differences in ligand topology. Distortion from regular octahedral geometry is minor for complexes of ligand L(2), but becomes significant in the complexes of the cyclic ligand L(1), where trans elongation of Fe-N bonds cannot be compensated by the rigid ligand backbone. This provokes trigonal twisting of the ligand field. This distortion causes the metal ion in complexes of L(1) to experience a significantly weaker ligand field than in the complexes of L(2), which are more regular. The reduced ligand-field strength in complexes of L(1) translates into a marked preference for the electronic high-spin state, the emergence of conformational isomers, and massively enhanced lability with respect to ligand exchange and oxidation of the central ion. Accordingly, oxoiron(IV) species derived from L(1) and L(2) differ in their spectroscopic properties and their chemical reactivity.