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

• Published in: Organic 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
• Language: English
• Published: United States American Chemical Society 03.06.2022
• Subjects: carbon-hydrogen bond activation; decarboxylation; hybridization; hydrogen; moieties

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...