Matrix isolation infrared spectroscopic study of the photochemistry of bis(cyclopentadienyl)dicarbonyl titanium in solid nitrogen

摘要： Infrared spectra of the photochemical products of bis(cyclopentadienyl)dicarbonyl titanium, TiCp2(CO)2, isolated in an Ar matrix and a N2 matrix were measured. UV-irradiation of TiCp2(CO)2 produced TiCp2(CO) in the Ar matrix, and three types of nitrogen-containing compounds, TiCp2(CO)(N2), TiCp2(N2), and TiCp2(N2)2 were produced in the N2 matrix. The yields of the species changed with the duration of UV-irradiation. Annealing of the sample resulted in the disappearance of unstable TiCp2(N2) and an increase of TiCp2(N2)2. Isotope shifts of the IR spectra were measured using 15N2 to confirm the assignments. The structures of the species were estimated using a double hybrid density functional theory calculation (mPW2PLYP/cc-pVTZ), and the calculated infrared frequencies were in very good agreement with the experimentally measured spectra.