RESUMO
The reversible methanolysis of an azomethine C[double bond, length as m-dash]N in a series of copper(ii) Schiff base complexes has been investigated through combined spectroscopic, structural, and kinetic studies. Pentadentate copper(ii) complexes [L1-Cu(X)]Y (L1 = 1,2-bis[(1-methyl-2-imidazolyl)methyleneamino]ethane; X = Y = ClO4- (1); X = Y = TfO- (2); X = Y = BF4- (3); X = H2O, Y = (ClO4-)2 (4) spontaneously add methanol in a ligand centered reaction to yield stable, isolable hemiaminal ether product complexes 5-8. In methanol free solution, 5-8 spontaneously release alcohol to regenerate 1-4. The methanol addition reaction is first-order in methanol and first-order in complex with second-order rate constants varying from 1.1 × 10-4 to 187 × 10-4 M-1 s-1 dependent on the donor ability of the axial ligand. Rate constants for methanol elimination vary from 0.67 to 3.7 × 10-4 s-1 with dependence on the counterion and water content of the solvent. Equilibrium constants for methanolysis range from 1.5 to 51 M-1. Structural comparisons of the Schiff base complexes 1-4 and the hemiaminal ether complexes 5-8 suggest methanol addition is favored by the release of ligand strain associated with three planar five-membered chelates in 1-4.
