The influence of the alkali metal cation is a distinctive aspect of the work reported here, and it pushes forward the growing understanding of the potential tuning role of cations near a transition-metal center. In a relevant example, Yang has shown that appended cations cause substantial electric fields, which can have beneficial influences on catalysis. Electronic structure calculations in these systems did not show that the orbital energies were differentially affected by the cation, leading to the conclusion that the cation mainly exerts an electrostatic effect.