Kinetics and mechanism of the amine exchange reactions of 2‐aminopyridine derived Schiff‐base ligands and their copper(II) complexes

The kinetics and product analyses of the amine exchange reactions of two 2‐aminopyridine derived Schiff‐base ligands and their monomeric bischelate and dimeric copper(II) complexes have been studied. The Schiff‐base ligands investigated underwent amine exchange reactions with n‐butyl, cyclohexyl, t‐butyl amines. The coordination of the Schiff‐base ligands to copper(II) rendered the amine exchange reactions slower. With n‐butyl and cyclohexyl amines, parallel first‐ and second‐order terms on their concentrations are observed for the amine exchange reactions of copper(II) bischelates and dimer. The kinetic data favor a mechanism involving a rate‐limiting elimination of 2‐aminopyridine from a diaminoacetal intermediate in preference to a scheme in which a dissociation of the complexes into free ligands and Cu(II) may precede the amine exchange. The steric factors influence the amine exchange reactions of Cu(II) bischelates with the bulkier amines reacting slower as given by the order t‐butylamine (3.3 ± 0.3 × 10−3 dm3/mol·s) < cyclohexylamine (0.2 ± 0.03 dm3/mol·s) < n‐butylamine (2.2 ± 0.2 dm3/mol·s). The bulkiness of the t‐butyl group and the constraints imposed by the changes in the coordination geometry of Cu(II) on amine exchange not only render the reactions of Cu(II) bischelates slower but also make the formation of the mixed adduct ([N‐(5‐methyl)‐2‐pyridyl salicylaldimine][N‐t‐butyl salicylaldimine] Cu(II)) more favored.