Deoxyhalogenation with Cu(III) Halide Complexes.
- 1Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio43210, United States.
Abstract
While high-valent metal-halide complexes are widely studied as oxidants that promote C-H activation, their Lewis acidic reactivity has received little attention. Herein, we report a new mode of Cu(III) reactivity in which Lewis acidic Cu(III) complexes activate C(sp3)-OH bond in alcohols and convert them to the corresponding alkyl fluorides, chlorides, and bromides. A series of formal Cu(III) halide complexes (X = F, Cl, Br) supported by the tris(2-pyridylthio)methanide (TPTM, L) ligand were synthesized. These trigonal-bipyramidal [LCuIII-X]+ complexes feature an anionic carbon donor trans to the halide, resulting in weakened Cu-X bonds. Unlike conventional Cu(III) complexes that typically promote hydrogen atom abstraction, [LCuIII-X]+ instead activates the C(sp3)-OH bond for deoxyhalogenation. Mechanistic studies suggest that the reaction proceeds through initial activation of the C(sp3)-OH bond by the Lewis acidic CuIII center to generate a carbocation intermediate, which is subsequently trapped by halides to form the C(sp3)-X bond. While Lewis acid-promoted deoxychlorination and deoxybromination reactions have been reported previously, this study represents the first example of a metal complex capable of mediating a general deoxyhalogenation series including F, Cl, and Br transfer.
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BibTeX
@article{queener2026deoxyhalogenation,
title = {{Deoxyhalogenation with Cu(III) Halide Complexes.}},
author = {Joshua A Queener and Ashleigh N Sherman and Abigail M Houser and Shiyu Zhang},
journal = {Inorganic chemistry},
year = {2026},
month = sep,
doi = {10.1021/acs.inorgchem.6c03041},
url = {https://europepmc.org/article/MED/42916477},
note = {CC BY},
}
RIS
TY - JOUR
TI - Deoxyhalogenation with Cu(III) Halide Complexes.
AU - Joshua A Queener
AU - Ashleigh N Sherman
AU - Abigail M Houser
AU - Shiyu Zhang
PY - 2026
DA - 2026/09/01
JO - Inorganic chemistry
DO - 10.1021/acs.inorgchem.6c03041
UR - https://europepmc.org/article/MED/42916477
AB - While high-valent metal-halide complexes are widely studied as oxidants that promote C-H activation, their Lewis acidic reactivity has received little attention. Herein, we report a new mode of Cu(III) reactivity in which Lewis acidic Cu(III) complexes activate C(sp3)-OH bond in alcohols and convert them to the corresponding alkyl fluorides, chlorides, and bromides. A series of formal Cu(III) halide complexes (X = F, Cl, Br) supported by the tris(2-pyridylthio)methanide (TPTM, L) ligand were synthesized. These trigonal-bipyramidal [LCuIII-X]+ complexes feature an anionic carbon donor trans to the halide, resulting in weakened Cu-X bonds. Unlike conventional Cu(III) complexes that typically promote hydrogen atom abstraction, [LCuIII-X]+ instead activates the C(sp3)-OH bond for deoxyhalogenation. Mechanistic studies suggest that the reaction proceeds through initial activation of the C(sp3)-OH bond by the Lewis acidic CuIII center to generate a carbocation intermediate, which is subsequently trapped by halides to form the C(sp3)-X bond. While Lewis acid-promoted deoxychlorination and deoxybromination reactions have been reported previously, this study represents the first example of a metal complex capable of mediating a general deoxyhalogenation series including F, Cl, and Br transfer.
SN - 0020-1669
SN - 1520-510X
ER -