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Dioxygen Reactivity Models for Cytochrome C Oxidase: Synthesis and Characterization of Oxo and Hydroxo-Bridged Porphyrin-Iron/Copper Dinuclear Complexes

  • Chapter
The Activation of Dioxygen and Homogeneous Catalytic Oxidation

Abstract

The synthesis of appropriate transition-metal complexes to model the structural, spectroscopic, and magnetic properties of a metalloprotein active-site provides an opportunity to consider the function and associated mechanism of that metalloprotein at the molecular level. One nice example is the dinuclear cuprous amine-bis-pyridyl complex, which effects arene hydroxylation (albeit of the ligand m-xylyl spacer) using molecular oxygen (O2).1 This extraordinary reaction involves cleavage of the O-O bond and subsequent insertion of an oxygen atom into an arene C-H bond under essentially ambient conditions, to model the function of copper monooxygenases such as tyrosinase. Another excellent example is the generation of dicupric trans-µ-1,2-peroxo complexes from cuprous precursors and O2, reversibly,2–4 to model the oxygen-transport property of the protein hemocyanin, which subsequently was discovered to bind O2 in η2:η2 fashion, as shown in Figure 1.4 The metalloprotein cytochrome c oxidase,5 however, due to its combination of diverse and unusual active-site metal centers, has eluded a convincing model description. As for its function, it probably binds O2 at a dinuclear site comprising heme-iron and histidyl-copper coordination; it then cleaves the O-O bond, via reduction, (vide infra ).5 The structural changes associated with this dinuclear site during turnover, and the intermediates produced therefrom, are by no means clearly understood. In the resting state, the dinuclear site exhibits strong antiferromagnetic coupling (-J =200 cm-1) suggesting the involvement of a bridging ligand, often postulated as µ-sulfido, µ-chloro, or µ-hydroxo. Thus, we have endeavored to synthesize model complexes of this enigmatic dinuclear site.

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Authors and Affiliations

  1. Department of Chemistry, The Johns Hopkins University, Baltimore, MD, 21218, USA

    Alaganandan Nanthakumar, Stephen Fox, Sarwar M. Nasir, Natarajan Ravi, Boi H. Huynh, Robert D. Orosz & Kenneth D. Karlin

  2. Department of Physics, Emory University, Atlanta, Georgia, 30322, USA

    Edmund P. Day

  3. Department of Chemistry, Emory University, Atlanta, Georgia, 30322, USA

    Karl S. Hagen

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  1. Alaganandan Nanthakumar
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  1. Texas A&M University, College Station, Texas, USA

    Derek H. R. Barton , Arthur E. Martell  & Donald T. Sawyer ,  & 

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Nanthakumar, A. et al. (1993). Dioxygen Reactivity Models for Cytochrome C Oxidase: Synthesis and Characterization of Oxo and Hydroxo-Bridged Porphyrin-Iron/Copper Dinuclear Complexes. In: Barton, D.H.R., Martell, A.E., Sawyer, D.T. (eds) The Activation of Dioxygen and Homogeneous Catalytic Oxidation. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-3000-8_27

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