Cu(II)-promoted methanolysis of N,N-dipicolylacetamide. multistep activation by decoupling of > ̈̈N-C═O resonance via Cu(II)-N binding, delivery of the Cu(II):((-)OCH3) nucleophile, and metal ion assistance of the departure of the leaving group.

The methanolysis of the Cu(II) complex of N-acetyl-N,N-bis(2-picolyl)amine (2) was investigated by a kinetic study as a function of pH in methanol at 25 °C and computationally by DFT calculations. The active species is the basic form of the complex (3(-)), or (1:Cu(II))((-)OCH(3))(HOCH(3))), and the rate constant for its solvolysis is k(max) = 1.5 × 10(-4) s(-1). The mechanism involves Cu(II) binding to the amide N lone pair, decoupling it from >N-C═O resonance, concomitant with Cu(II):((-)OCH(3)) delivery to the adjacent >N-C═O unit, followed by Cu(II)-assisted departure of the N,N-bis(2-picolyl)amide from a tetrahedral intermediate.