Group 6 metal atoms, generated by laser ablation, react with CO2 to give the insertion products OMCO and O2M(CO)(2) (M = Cr, Mo, or W) which have been isolated in argon matrices and identified by the effects of isotopic substitution on their infrared spectra. These assignments have been supported by DFT calculations, and the theoretical and experimental spectra are in excellent agreement. Other products include the molecules O2MCO, MO, and MCO and the CO2 complex Cr (eta(1)-OCO) which, upon irradiation with UV-light, will photoisomerize to give OCrCO, an interesting example of photoactivation of CO2.