Stopped-Flow and DFT Studies of Proton Transfer and Isomerization of 5-Amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine and Its Related Base 2-(5-Amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide in Water: A Completely Sorted out Square Scheme

International audience; A complete kinetic study of pH-dependent isomerization of 5-amino-3-imino-1,2,6,7-tetracyano-3H-pyrrolizine (HL) and 2-(5-amino-3,4-dicyano-2H-pyrrol-2-ylidene)-1,1,2-tricyanoethanide (L‘-) in the pH range from −0.5 to +13 in aqueous solution, which spans over 7 orders of magnitude for the pseudo-first-order rates (log k from −4.8 to +2.5), has revealed for the first time the existence of the corresponding conjugate species L- and HL‘. The study has allowed the determination of the acid dissociation constants of HL (pKa) and HL‘ (pKa‘), as well as all of the individual forward and reverse isomerization rates of the acidic (HL/HL‘) and basic (L-/L‘-) forms. Although L…