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Issue 14, 2018
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Diverse copper(III) trifluoromethyl complexes with mono-, bi- and tridentate ligands and their versatile reactivity

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Abstract

Cu(III) trifluoromethyl complexes are proposed as essential intermediates for many copper-promoted trifluoromethylation reactions, but remain elusive and scarcely explored. We report herein the isolation and spectroscopic and X-ray crystallographic characterization of diverse CuIII–CF3 complexes (6–10) with varied coordinating motifs (mono-, bi- or tridentate) and formal charges (neutral or monoanionic) for the ligand L (L is pyridine, 2,4,6-trimethylpyridine, quinol-8-yloxide or 2,6-bis(2′-pyridyl)pyridine). Square planar complexes 6, 7 and 9 show rapid dynamic behavior in solution possibly due to the weak Cu–CF3 bonds that can quickly dissociate and recombine with the CF3 radical. In contrast, 10, with octahedral geometry, is more rigid. Reactivity studies show that except for ion-pair complex 8, they are highly reactive for the trifluoromethylation of arylboronic acids and the C–H bond of terminal alkynes. Furthermore, syn-fluoro- and -oxy-trifluoromethylation across the triple bond of alkynes can be achieved using 6 and CsF or NaOPh. These results greatly expand the scope of isolated and well-characterized Cu(III)–CF3 complexes, and establish their versatile reactivity that may be widely involved in copper-mediated trifluoromethylation reactions, thus substantiating the essential yet undeveloped aspects of trifluoromethylation chemistry.

Graphical abstract: Diverse copper(iii) trifluoromethyl complexes with mono-, bi- and tridentate ligands and their versatile reactivity

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Publication details

The article was received on 23 Jan 2018, accepted on 27 Feb 2018 and first published on 27 Feb 2018


Article type: Communication
DOI: 10.1039/C8DT00291F
Citation: Dalton Trans., 2018,47, 4779-4784
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    Diverse copper(III) trifluoromethyl complexes with mono-, bi- and tridentate ligands and their versatile reactivity

    S. Zhang, C. Xiao and H. Wan, Dalton Trans., 2018, 47, 4779
    DOI: 10.1039/C8DT00291F

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