Zinc complexes of three new amide-appended ligands have been prepared and isolated. These complexes, [(dpppa)Zn](ClO4)(2) (4(ClO4)(2); dpppa = N-((N,N-diethylamino)ethyl)-N-((6-pivaloylamido-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine), [(bdppa)Zn](ClO4)(2) (6(ClO4)(2); bdppa = N,N-bis((N,N-diethylamino)ethyl)-N-((6-pivaloylamido-2-pyridyl)methyl)am ine), and [(epppa)Zn](ClO4)(2) (8(ClO4)(2); epppa = N-((2-ethylthio)ethyl)-N-((6-pivaloylamido-2-pyridyl)methyl)-N-((2-pyrid yl)methyl)amine), have been characterized by X-ray crystallography (4(ClO4)(2) and 8(ClO4)(2)), H-1 and C-13 NMR, IR, and elemental analysis. Treatment of 8(ClO4)(2) or 8(ClO4)(2) with 1 equiv of Me4NOH center dot 5H(2)O in methanol-acetonitrile (5:3) results in amide methanolysis, as determined by the recovery of primary amine-appended forms of the chelate ligand following removal of the zinc ion. These reactions proceed via the initial formation of a deprotonated amide intermediate ([(dpppa(-))Zn]ClO4 (5) and [(epppa(-))Zn]ClO4 (9)) which in each case has been isolated and characterized (H-1 and C-13 NMR, IR, elemental analysis). Treatment of 6(ClO4)(2) with Me4NOH center dot 5H(2)O in methanol-acetonitrile results in the formation of a deprotonated amide complex, [(bdppa(-))Zn]ClO4 (7), which was isolated and characterized. This complex does not undergo amide methanolysis after prolonged heating in a methanol-acetonitrile mixture. Kinetic studies and construction of Eyring plots for the amide methanolysis reactions of 4(ClO4)(2) and 8(ClO4)(2) yielded thermodynamic parameters that provide a rationale for the relative rates of the amide methanolysis reactions. Overall, we propose that the mechanistic pathway for these amide methanolysis reactions involves reaction of the deprotonated amide complex with methanol to produce a zinc methoxide species, the reactivity of which depends, at least in part, on the steric hindrance imparted by the supporting chelate ligand. Amide methanolysis involving a zinc complex supported by a N2S2 donor chelate ligand (3(ClO4)(2)) is more complicated, as in addition to the formation of a deprotonated amide intermediate free chelate ligand is present in the reaction mixture.