The electronic structures of the prototypical bimetallic buta-1,3-diyn-1,4-diyl-bridged radical cation complexes [{M(dppe)Cp'}(2)(mu-C CC C)](+) (M= Fe, Cp' = Cp* (1a), Cp (1b); M = Ru, Cp' = Cp* (2a), Cp (2b)) have been (re)investigated using a combination of UV-vis-NIR and IR spectroelectrochemistry, and quantum chemical calculations based on both dispersion-corrected global (BLYP35-D3) and local (Lh-SsirPW92-D3) hybrid functionals. Following analysis of new and existing data, including the IR-active v(C C) bands, the iron compounds [1](+) are reclassified as valence-trapped (Robin and Day Class II) mixed-valence complexes, in contrast to the ruthenium complexes [2](+), which are delocalized (Robin and Day Class III) systems. All members of the series exist as a thermally populated distribution of conformers in solution, and the overlapping spectroscopic profiles make the accurate extraction of the parameters necessary for the analysis of [1](+) and [2](+) within the framework of the Marcus-Hush model extremely challenging. Analysis of the spin-density distributions from a range of conformational minima provides an alternative representation of the degree of charge localization, and a comparison between members of the series is presented.