Nucleophilic Reactivity of a Copper(II)–Superoxide Complex |
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| Authors: | Paolo Pirovano Adriana M Magherusan Ciara McGlynn Andrew Ure Amy Lynes Dr Aidan R McDonald |
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| Affiliation: | School of Chemistry and CRANN/AMBER Nanoscience Institute, Trinity College Dublin, College Green, Dublin 2 (Ireland) http://www.tcd.ie/Chemistry/staff/people/mcdonald/ |
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| Abstract: | Metal‐bound superoxide intermediates are often implicated as electrophilic oxidants in dioxygen‐activating metalloenzymes. In the nonheme iron α‐ketoglutarate dependent oxygenases and pterin‐dependent hydroxylases, however, FeIII–superoxide intermediates are postulated to react by nucleophilic attack on electrophilic carbon atoms. By reacting a CuII–superoxide complex ( 1 ) with acyl chloride substrates, we have found that a metal–superoxide complex can be a very reactive nucleophile. Furthermore, 1 was found to be an efficient nucleophilic deformylating reagent, capable of Baeyer–Villiger oxidation of a number of aldehyde substrates. The observed nucleophilic chemistry represents a new domain for metal–superoxide reactivity. Our observations provide support for the postulated role of metal–superoxide intermediates in nonheme iron α‐ketoglutarate dependent and pterin‐dependent enzymes. |
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| Keywords: | bioinorganic chemistry dioxygen activation nucleophilic reactivity reaction mechanisms superoxide complexes |
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