Co+(C2H2)n (n = 1-6) complexes produced with laser vaporization in a supersonic molecular beam are studied with infrared photodissociation spectroscopy and computational chemistry. Infrared spectra are measured in the C-H stretching region using the method of tagging with argon atoms to enhance the photodissociation yields. C-H stretch vibrations for all clusters studied are shifted to lower frequencies than those of the well-known acetylene vibrations from ligand → metal charge transfer interactions. The magnitude of the red shifts decreases in the larger clusters as the interaction is distributed over more ligands. Computational studies identify various unreacted complexes with individual acetylene ligands in cation-π bonding configurations as well as reacted isomers in which ligand coupling reactions have taken place. Infrared spectra are consistent only with unreacted structures, even though the formation of reacted structures such as the metal ion-benzene complex is highly exothermic. Large activation barriers are predicted by theory along the reaction coordinates for the n = 2 and 3 complexes, which inhibit reactions in these smaller clusters, and this situation is presumed to persist in larger clusters.