The chemistry of mixed-valence complexes joins that of molecular electronics in the quantum cellular automata (QCA) paradigm, a concept which has been demonstrated to be a possible alternative to the transistor-based technology, in which binary information is encoded in the configuration of charge among redox-active molecular sites. Experimental and theoretical efforts have recently been devoted to molecular mixed-valence organometallic systems containing two and four metal centers as candidates for QCA. Properties of specific examples based on hypothetical organometallic molecules are theoretically analyzed and discussed with the aid of DFT calculations.