In this article, we resort to first-principles molecular dynamic simulations to examine the thermal effects on the structure of [Pb(CO)(n)](2+) complexes. Values of n are chosen to sample structures where hemidirected (n = 2, 4 and 6) or holodirected (n = 7 and 8) structures are found when using static approaches. In all cases, highly flexible structures are observed. In particular, hemidirectional distortions are characterized using geometrical and topological analysis. The octacarbonyl complex exhibits the decoordination of one of its carbonyl ligands at 300 K.