Matrix infrared spectroscopy and density functional theory calculations of novel transition metal-containing molecules

The infrared spectra of the matrix-isolated products from the reactions between laser-ablated transition metal atoms and small molecules are observed. Density functional theory calculations are performed on these first-ever compounds, and the calculated harmonic vibrational frequencies support the experimental assignments. Bonding interactions and reaction mechanisms are discussed.; In the reactions between Group 10 and 11 transition metals and CO, carbonyl cations and anions, as well as neutrals, are observed and analyzed. Generally, the carbonyl stretching mode is in the order cation > neutral > anion, which reveals distinct bonding differences in these complexes.; Reactions between laser-ablated Re, Ru and Os atoms and CO₂ produce the primary insertion reaction product OMCO. However, different products are found in the reactions between primary product OMCO and the second CO ₂ molecule.; Systematic investigation of Group 4, 5, and 6 transition metal sulfides observes vibrational frequencies for the isolated MS₂ molecules. Based on the isotopic frequencies, the S-M-S bond angles are determined. Evidence for several metal monosulfides and trisulfides is also presented.; The cis- and trans-OONO− anions formed in the reaction between NO and O₂− are isolated in the 7 K argon matrix. These two isomers are reversibly photoisomerized by visible and near-UV irradiation. DFT calculated frequencies support these findings.