OXALATE FORMATION IN TITANIUM-CARBON DIOXIDE ANIONIC CLUSTERS STUDIED BY INFRARED PHOTODISSOCIATION SPECTROSCOPY

Carbon-carbon bond formation during carbon dioxide fixation would enable bulk synthesis of hydrocarbon chains, generally through formation of an oxalate intermediate. In this talk, we demonstrate the formation of $[text{Ti}(text{CO}_{2})_{y}]^{-}$ ($y$ = $4-6$) gas phase clusters with an oxalate ligand bearing significant ($> 1$ e$^{-}$) negative charge. Gas phase anionic clusters were generated using laser ablation of a titanium metal target in the presence of a CO$_{2}$ expansion, and the infrared photodissociation spectra were measured from $950-2400$ cm$^{-1}$, revealing vibrations characteristic of the oxalate anion. The molecular structure of these clusters was identified by comparing the experimental vibrational spectra with density functional theory calculations