A Unified Approach to CO₂–Amine Reaction Mechanisms

A unified CO₂-amine reaction mechanism applicable to absorption in aqueous or nonaqueous solutions and to adsorption on immobilized amines in the presence of both dry and humid conditions is proposed. Key findings supported by theoretical calculations and experimental evidence are as follows: (1) The formation of the 1,3-zwitterion, RH₂N⁺-COO⁻, is highly unlikely because not only the associated four-membered mechanism has a high energy barrier, but also it is not consistent with the orbital symmetry requirements for chemical reactions. (2) The nucleophilic attack of CO₂ by amines requires the catalytic assistance of a Bro̷nsted base through a six-membered mechanism to achieve proton transfer/exchange. An important consequence of this concerted mechanism is that the N and H atoms added to the C=O double bond do not originate from a single amine group. Using ethylenediamine for illustration, detailed description of the reaction pathway is reported using the reactive internal reaction coordinate as a new tool to visualize the reaction path. (3) In the presence of protic amines, the formation of ammonium bicarbonate/carbonate does not take place through the widely accepted hydration of carbamate/carbamic acid. Instead, water behaves as a nucleophile that attacks CO₂ with catalytic assistance by amine groups, and carbamate/carbamic acid decomposes back to amine and CO₂. (4) Generalization of the catalytic assistance concept to any Bro̷nsted base established through theoretical calculations was supported by infrared measurements. A unified six-membered mechanism was proposed to describe all possible interactions of CO₂ with amines and water, each playing the role of a nucleophile and/or Bro̷nsted base, depending on the actual conditions.