Carboxylate as a Non-innocent L‑Ligand: Computational and Experimental Search for Metal-Bound Carboxylate Radicals

We show that the carboxylate radical acts as an L-ligand with certain high-spin transition metal centers. Such coordination preserves the O-radical character needed for C–H activation via hydrogen atom transfer. Capture of the new C-radical by the metal and subsequent reductive elimination leads to...

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Published inOrganic letters Vol. 24; no. 21; pp. 3817 - 3822
Main Authors Kuhn, Leah, Vil’, Vera A., Barsegyan, Yana A., Terent’ev, Alexander O., Alabugin, Igor V.
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 03.06.2022
Subjects
carbon-hydrogen bond activation
decarboxylation
hybridization
hydrogen
moieties
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Summary:We show that the carboxylate radical acts as an L-ligand with certain high-spin transition metal centers. Such coordination preserves the O-radical character needed for C–H activation via hydrogen atom transfer. Capture of the new C-radical by the metal and subsequent reductive elimination leads to formal C–H acyloxylation. Decarboxylation of the RCO2 radical is minimized through hybridization effects introduced by spiro-cyclopropyl moiety.
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ISSN:1523-7060
1523-7052
1523-7052
DOI:10.1021/acs.orglett.2c01356