Formally Copper(III)-Alkylperoxo Complexes as Models of Possible Intermediates in Monooxygenase Enzymes.

Reaction of [NBu][LCuOH] with excess ROOH (R = cumyl or tBu) yielded [NBu][LCuOOR], the reversible one-electron oxidation of which generated novel species with [CuOOR] cores (formally CuOOR), identified by spectroscopy and theory for the case R = cumyl. This species reacts with weak O-H bonds in TEMPO-H and 4-dimethylaminophenol (PhOH), the latter yielding LCu(OPh), which was also prepared independently. With the identification of [CuOOR] complexes, the first precedent for this core in enzymes is provided, with implications for copper monooxygenase mechanisms.