This work is a mechanistic study of the CO2 reaction with diamines under both dry and wet conditions. All protic α,ω-diamines R1H1N1-(CH2)n-N2H2R2, with n = 1-5 and R1 and R2 = H and/or CH3, were investigated. Depending on the nature of the diamine, the reaction was found to follow one of two concerted asynchronous reaction mechanisms with a zwitterion hidden intermediate. Both mechanisms involved two processes. The first process consisted of a nucleophilic attack of the nitrogen N1 of the first amine group on the carbon of CO2, accompanied by the transfer of a hydrogen atom H1 from N1 to the nitrogen N2 of the second amine group, leading to the formation of a carbamate zwitterion. The subsequent process corresponds to the transfer of a hydrogen atom H2 from the second amine group N2 to an oxygen atom of CO2, thus ending the reaction by the formation of carbamic acid. The structure of the zwitterion hidden intermediate was determined using the reactive internal reaction coordinates (RIRC), a reaction pathway visualization tool, consisting of a 3D representation of the potential energy versus the internuclear distances N2-H1 and N2-H2, which correspond to the bond being formed and the bond being broken, respectively. The life span of the transitory species, i.e., the zwitterion, was found to depend on the nature of the second amine group. For primary amines, the life span of the zwitterion was "short", whereas for secondary amines, it was "long". The corresponding mechanisms were termed the "early" and "late" asynchronous mechanism, respectively. Regardless of the mechanism, the activation barriers were found to decrease with the length of the carbon chain linking the two amine groups, with an asymptotic behavior from n = 4. Involvement of a water molecule generates a significant catalytic effect for diamines with short carbon chains (n < 4), whereas for longer chain diamines, water has a slightly adverse effect.