A Tricopper(I) Complex Competent for O Atom Transfer, C–H Bond Activation, and Multiple O2 Activation Steps

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Abstract
Oxygenation of a tricopper(I) cyclophanate (1) affords reactive transients competent for C–H bond activation and O atom transfer to various substrates (including toluene, dihydroanthracene, and ethylmethylsulfide) based on 1H NMR, gas chromatography/mass spectrometry (MS), and electrospray ionization (ESI)/MS data. Low product yields (1H NMR, and density functional theory (DFT) results for reaction of 1 with O2 are consistent with transient peroxo- and di(oxo)-bridged intermediates. DFT calculations elucidate a concerted proton-coupled electron transfer from toluene to the di(μ-oxo) intermediate and subsequent radical rebound as the C–H activation mechanism. Our results support a multicopper oxidase-like mechanism for O2 activation by 1, traversing species similar to the coplanar Cu3O2 unit in the peroxy and native intermediates.
Funding Information
  • Division of Chemistry (CHE-1048604, CHE-1464876)
  • American Chemical Society Petroleum Research Fund (52704-DNI3)
  • National Institute of General Medical Sciences (R01GM123241)

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