Abstract
THE unlikelihood of determining the geometry of coordinated dioxygen in oxyhaemoglobin and oxymyoglobin by X-ray crystallographic techniques has prompted great interest in simpler model systems1–4 and a great deal of theoretical speculation5–9. The mode of coordination of dioxygen and the related peroxo (O22−) and superoxo (O2−) ligands depends on the metal atom in the model complex. Platinum metal tertiaryphosphine dioxygen1,2 and chromium molybdenum and titanium peroxo-complexes10–12 have the dioxygen moiety symmetrically (π) bonded (Fig. la) and cobalt (III) amine and Schiff base peroxo and superoxo-complexes, which are usually binuclear, have the less symmetrical geometry3,13,14 shown in Fig. \b. The absence of a bonding scheme which explains these different geometries has severely limited their evaluation as model systems. (The diamagnetism of oxyhaemoglobin precludes a linear Fe-O-O geometry7.)
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MINGOS, D. Geometries of Dioxygen (O2), Superoxo (O2−) and Peroxo (O22−) Complexes. Nature Physical Science 230, 154–156 (1971). https://doi.org/10.1038/physci230154a0
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DOI: https://doi.org/10.1038/physci230154a0
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