Treatment of [(ppbpa)Zn](ClO4)2 (11 (ClO4)2, Ppbpa = N-((6-(pivaloylamido)-2-pyridyl)methyl)-N,N-bis((2-pyridyl)methyl)amine) with 1 equiv of Me4NOH center dot 5H(2)O in methanol-acetonitrile solution results within minutes in the stoichiometric formation of a complex having a deprotonated amide, [(ppbpa(-))Zn]ClO4 (3). Complex 3 has been characterized by H-1 and C-13 NMR, FTIR, and elemental analysis. Notably, upfield shifts of specific H-1 NMR resonances of the amide-appended pyridyl moiety in 3, versus those found for 1(ClO4)(2), indicate delocalization of the anionic charge within the amide-appended pyridyl donor of this complex. Heating of analytically pure 3 in methanol-acetonitrile results in amide alcoholysis. Overall, this alcoholysis reaction is second-order, with a first-order dependence on both 3 and methanol. Analysis of the rate of decay of 3 as a function of temperature yielded activation parameters consistent with an intramolecular amide cleavage process (Delta H-double dagger = 15.0(3) kcal/mol, Delta S-double dagger = -33(1) eu). A possible reaction mechanism for amide alcoholysis is presented which involves reaction of the deprotonated amide intermediate 3 with methanol to produce a Lewis activated-type structure from which amide cleavage may be initiated. Additional support for this mechanistic pathway has been obtained through examination of the analogous ethanolysis reaction and via evaluation of the effect of varying steric hindrance near the amide carbonyl unit.