Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 139, Issue 30, Pages 10220-10223Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b05754
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- NSF-MRI [CHE-1229400]
- NIH [R37GM47365]
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Reaction of [NBu4][(LCuOH)-O-II] with excess ROOH (R = cumyl or tBu) yielded [NBu4] [(LCuOOR)-O-II, the reversible one-electron oxidation of which generated novel species with [CuOQR](2+) cores (formally (CuOOR)-O-III), 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)-Ph-Nme2), 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.
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