Abstract
Reaction of [NBu
][LCu
OH] with excess ROOH (R = cumyl or tBu) yielded [NBu
][LCu
OOR], the reversible one-electron oxidation of which generated novel species with [CuOOR]
cores (formally Cu
OOR), 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.