A simple tight-binding model is used to study electronic distributions and Peierls distortions in a series of mixed-valence linear-chain complexes [Mn-II(LL)(2)][M(IV)(LL)(2)X(2)] (M = Ni, Pd, Pt; X = Cl, Pr, I; LL = 1,2-diaminoethane, 2,3-diaminopropane). The calculated values of Peierls distortions for complexes with known structure are in good agreement with the experimental data. For the whole series, the model is employed as a qualitative tool to analyze structural and electronic properties. It is shown that charge disproportionation occurs in the related dimers. Thus, our quantum chemical calculations as well as previous phenomenological approaches indicate that, in metal-halogen chains, one deals with the interplay of local and cooperative effects.