Formally Copper(III) Alkylperoxo Complexes as Models of Possible Intermediates in Monooxygenase Enzymes.
Reaction of [NBu4][LCuIIOH] with excess ROOH (R cumyl or tBu) yielded [NBu4][LCuIIOOR] the reversible one electron oxidation of which generated novel species with [CuOOR]2+ cores (formally CuIIIOOR) identified by spectroscopy and theory for the case R cumyl. This species reacts with weak O H bonds in TEMPO H and 4 dimethylaminophenol (NMe2PhOH) the latter yielding LCu(OPhNMe2) which was also prepared independently. With the identification of [CuOOR]2+ complexes, the first precedent for this core in enzymes is provided, with implications for copper monooxygenase mechanisms.
Journal of the American Chemical Society