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Dr. Matthew T. Kieber-Emmons, Munzarin F. Qayyum, Yuqi Li, Dr. Zakaria Halime, Prof. Keith O. Hodgson, Prof. Britt Hedman, Prof. Kenneth D. Karlin and Prof. Edward I. Solomon Spectroscopic Elucidation of a New Heme/Copper Dioxygen Structure Type: Implications for O⋅⋅⋅O Bond Rupture in Cytochrome c Oxidase Angewandte Chemie International Edition 51

Article first published online: 16 NOV 2011 | DOI: 10.1002/anie.201104080

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All's well that ends well: The geometric and electronic structure of the first end-on heme–peroxo–copper adduct (see picture) was elucidated using UV/Vis, resonance Raman, and X-ray absorption spectroscopy and is supported by DFT calculations. Coordination of the axial base is correlated to a spin-state change, leading to enhanced biomimetic reactivity, and gives insight into O[BOND]O bond cleavage by cytochrome c oxidase.

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