Interrogating the Carboxylation of Potassium β-Diketonates and β-Diketiminates by Carbon Dioxide

Enolate carboxylation by CO₂ is essential to applications ranging from polymer synthesis to CO₂ capture, yet the CO₂ reactivity of stabilized enolates, such as β-dicarbonyl enolates, remains understudied. Combining detailed NMR and DFT studies, we report the reactivity of diverse potassium β-diketonates and β-diketiminates toward CO₂. Our findings reveal the critical role of β'-substituents on β-diketiminates and an unexpected CO₂-concentration-dependent reactivity switch, offering structural insights for designing materials with tunable CO₂ reactivity.