We present a detailed theoretical study of the pathway for water oxidation in synthetic ruthenium-based catalysts. As a first step, we consider a recently discovered single center catalyst, where experimental observations suggest a purely single-center mechanism. We find low activation energies (<5 kcal/mol) for each rearrangement in the catalytic cycle. In the crucial step of O-O bond formation, a solvent water acts as a Lewis base and attacks a highly oxidized Ru-V=O. Armed with the structures and energetics of the single-center catalyst, we proceed to consider a representative Ru-dimer which was designed to form O-2 via coupling between the two centers. We discover a mechanism that proceeds in analogous fashion to the monomer case, with all the most significant steps occurring at a single catalytic center within the dimer. This acid base mechanism suggests a new set of strategies for the rational design of multicenter catalysts: rather than coordinating the relative orientations of the subunits, one can focus on coordinating solvation-shell water molecules or tuning redox potentials.