Carboxylate as a Non-innocent L-Ligand: Computational and Experimental Search for Metal-Bound Carboxylate Radicals
Leah Kuhn, Vera A. Vil’, Yana A. Barsegyan, Alexander O. Terent’ev, Igor V. Alabugin
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.
Topics & Concepts
ChemistryCarboxylateDecarboxylationMoietyRadicalLigand (biochemistry)MetalHydrogen atomPhotochemistryStereochemistryMedicinal chemistryCatalysisOrganic chemistryGroup (periodic table)ReceptorBiochemistryCatalytic C–H Functionalization MethodsRadical Photochemical ReactionsCyclopropane Reaction Mechanisms