A SPECTROSCOPIC AND THEORETICAL-STUDY OF THE REACTIONS OF GROUP-6 METAL ATOMS WITH CARBON-DIOXIDE

Group 6 metal atoms, generated by laser ablation, react with CO2 to gi ve 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 ha ve been supported by DFT calculations, and the theoretical and experim ental spectra are in excellent agreement. Other products include the m olecules 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.