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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Abstract 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.
AbstractList 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.
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.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.
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 RCO radical is minimized through hybridization effects introduced by spiro-cyclopropyl moiety.
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.
Author Alabugin, Igor V.
Vil’, Vera A.
Barsegyan, Yana A.
Kuhn, Leah
Terent’ev, Alexander O.
AuthorAffiliation Department of Chemistry and Biochemistry
N. D. Zelinsky Institute of Organic Chemistry
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Snippet 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...
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SubjectTerms carbon-hydrogen bond activation
decarboxylation
hybridization
hydrogen
moieties
Title Carboxylate as a Non-innocent L‑Ligand: Computational and Experimental Search for Metal-Bound Carboxylate Radicals
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