Using density functional theory (DFT), the effects of appended s-block metal ion crown ethers upon the redox properties of the following nitridomanganese(V) salen complexes were investigated: Rsalen)Mn-V(N)(Mn+-crown ether)](n+) (salen = N,N'-bis(salicydene)ethylenediamine; M = Na+, Ba2+, and Sr2+ for 1Na, 1K, 1Ba, and 1Sr, respectively; A = complex without Mn+-crown ether and B = without Mn+). NBO analysis of the MnN bond orders, optimized bond lengths, and stretching frequencies changes upon oxidation for all species show that for A, B, and 1Na MnN more nitridyl character while a nitride form is more significant for 1K, 1Ba, and 1Sr. The results reveal that Delta G(rxn)(e(-)) and thus E-1/2 are quite sensitive to the point charge (q) of the s-block metal ions (1 for K+/Na+ and 2 for Ba2+/Sr2+). Computations suggest that the degree of delocalization of the HOMO electrons on the supporting ligand is modified by the chelated s-block metal ion. Methane activation by A(center dot+), 1K(center dot+), and 1Ba(center dot+) complexes proceeds via a hydrogen atom transfer (HAT) pathway with reasonable barriers for all complexes with similar to 4 kcal/mol difference in energy. The molecular electrostatic potential (MEP) maps indicate a shift in redox potential imposed by the nonredox active cations by altering the electrostatic potential of the complexes. Computations show that the complexes with higher point charge of the incorporated metal ions result in higher N-H bond BDFEs. Changes in predicted properties as a function of continuum solvent dielectric constant suggest that the primary effect of the appended s-block ion is via "through space" interactions.