Formation and Oxidation of Metal-Based CO and CO2 Complexes: Characterization of Al(CO)x and Al(CO2)x and their Oxidation

Article abstract of DOI:10.1021/j100313a002

In a comparative study, aluminum atoms entrained in argon, CO, and CO2 are oxidized with ozone to inspect the nature of aluminum complexation with CO and CO2 to form Al(CO)x (x= 1, 2) and AlCO2 adducts.The optical signatures corresponding to the chemiluminescent oxidation of these complexes with ozone to form the AlO B²Σ⁺ state or, in the case of CO2, a polyatomic complex are compared to that AlO B²Σ⁺ emission associated with the chemiluminescent oxidation of nonbonded aluminum atoms in argon.We (1) establish a method for evaluating M(CO)x binding energies and (2) observe the optical signature for a potentially long-lived (ca. 1E-7 s) metal oxide-carbon dioxide solvation complex formed in metal-CO2 complex oxidation.From a comparison of these studies, with results obtained for Al-N2O oxidation, we estimate a lower bound to the total (Al(CO)2 binding energy (to Al+2CO) of ca.0.7 eV.The current study in conjunction with parallel efforts involving the transition metals suggests a method for studying the spectra of MCO, M(CO)2, and M-CO2 complexes.