Spectroscopic Identification of Carbamate Formation and Synergistic Binding in Amide–CO ₂ Complexes

Carbamate formation is an elementary step that governs nitrogen-centered nucleophilic CO₂ capture across diverse environments, yet a direct, structure-specific understanding has been lacking. Here, we report the first gas-phase characterization of closed-shell carbamate formation by deprotonated amides, using cryogenic ion trap vibrational spectroscopy combined with quantum chemical calculations. Reactions of deprotonated benzamide and isophthalamide anions with CO₂ form carbamate species, with the amide nitrogen serving as the nucleophilic site. Diagnostic, strongly red-shifted antisymmetric CO₂ stretching vibrational bands, supported by a bonding analysis, establish chemisorption with substantial charge transfer. In the multiamide system, an intramolecular N-H···O hydrogen bond provides synergistic stabilization, correlating with larger red shifts and more exothermic binding. These structure-assigned benchmarks provide molecular-level insights into the binding motif, charge redistribution, and hydrogen bond-mediated stabilization of amide carbamates, which aid the characterization of carbamate formation in condensed phase.