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• W3155776575 endingPage "7143" @default.
• W3155776575 startingPage "7135" @default.
• W3155776575 abstract "A dicopper nitrenoid complex was prepared by formal oxidative addition of the nitrenoid fragment to a dicopper(I) center by reaction with the iminoiodinane PhINTs (Ts = tosylate). This nitrenoid complex, (DPFN)Cu2(μ-NTs)[NTf2]2 (DPFN = 2,7-bis(fluorodi(2-pyridyl)methyl)-1,8-naphthyridine), is a powerful H atom abstractor that reacts with a range of strong C-H bonds to form a mixed-valence Cu(I)/Cu(II) μ-NHTs amido complex in the first example of a clean H atom transfer to a dicopper nitrenoid core. In line with this reactivity, DFT calculations reveal that the nitrenoid is best described as an iminyl (NR radical anion) complex. The nitrenoid was trapped by the addition of water to form a mixed-donor hydroxo/amido dicopper(II) complex, which was independently obtained by reaction of a Cu2(μ-OH)2 complex with an amine through a protonolysis pathway. This mixed-donor complex is an analogue for the proposed intermediate in copper-catalyzed Chan-Evans-Lam coupling, which proceeds via C-X (X = N or O) bond formation. Treatment of the dicopper(II) mixed donor complex with MgPh2(THF)2 resulted in generation of a mixture that includes both phenol and a previously reported dicopper(I) bridging phenyl complex, illustrating that both reduction of dicopper(II) to dicopper(I) and concomitant C-X bond formation are feasible." @default.
• W3155776575 created "2021-04-26" @default.
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• W3155776575 date "2021-04-20" @default.
• W3155776575 modified "2023-10-14" @default.
• W3155776575 title "A Dicopper Nitrenoid by Oxidation of a Cu^ICu^I Core: Synthesis, Electronic Structure, and Reactivity" @default.
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• W3155776575 doi "https://doi.org/10.1021/jacs.1c02235" @default.
• W3155776575 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/33877827" @default.
• W3155776575 hasPublicationYear "2021" @default.
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