Abstract
In contrast to imidazolyl−phenoxyl radical models for the putative histidinyl−tyrosyl radical intermediate in the catalytic cycle of cytochrome c oxidase (CcO), imidazolyl−semiquinone radicals are stable and may be quantitatively produced. Internal electron transfer (valence tautomerism) within a CuII−imidazolyl−hydroquinonate species formed upon deprotonation of the parent CuII−imidazolyl−hydroquinone complex results in a substitutionally labile CuI−imidazolyl−semiquinone radical system. The results show the potential reactivity of a (transient) CuBII−histidinyl−tyrosyl anion intermediate in the catalytic cycle of CcO.
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