Bond Insertion in Metal-Carbon Dioxide Anionic Clusters Studied by Infrared Photodissociation Spectroscopy

C-O bond breaking is an important process in the activation of CO_2 that can be catalyzed by the presence of a metal. In this talk, we investigate the factors that lead to bond insertion in [M(CO_2)_y]^- gas phase clusters, specifically addressing differences amongst the metals M = Ni, Fe, and Ti. Gas phase anionic clusters were generated using laser ablation of a metal target in the presence of a CO_2 expansion, and the infrared photodissociation spectra were measured from 950-2400 \wn. Metal carbonyl vibrational signatures were used to infer bond insertion, and computational chemistry simulations were used to assess the feasibility of bond breaking in these systems.