Interactions of Molecular Titanium Oxides TiOx (x = 1–3) with Carbon Dioxide in Cluster Anions

We study small titanium oxide–CO2 cluster anions in vacuo to understand the fundamental interactions between TiOx and CO2 in the presence of an excess electron. Infrared spectra of [TiOx(CO2)y]− (x = 1–3, y > 1) were obtained using photodissociation spectroscopy and assigned through quantum chemistry calculations, identifying the formation of carbonato, oxalato, oxo, η2-(O,O), and carbonyl ligands in the core ions of these clusters, with carbonato ligands being the dominant ligand species.