Experimental and Theoretical Study of the Structure and Reactivity of Fe_1-2O_≤6^- Clusters with CO

Synergistic studies employing experiments in the gas phase and theoretical first principles calculations have been carried out to investigate the structure, stability, and reactivity toward CO of iron oxide cluster anions, Fe_xO_y^- (x = 1−2, y ≤ 6). Collision-induced dissociation studies of iron oxide species, employing xenon collision gas, show that FeO₃^- and FeO₂^- are the stable building blocks of the larger iron oxide clusters. Theoretical calculations show that the fragmentation patterns leading to the production of O or FeO_n fragments are governed both by the energetics of the overall process as well as the number of intermediate states and the changes in spin multiplicity. Mass-selected experiments identified oxygen atom transfer to CO as the dominant reaction pathway for most anionic iron oxide clusters. A theoretical analysis of the molecular level pathways has been carried out to highlight the role of energetics as well as the spin states of the intermediates on the oxidation reaction.