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

Infrared spectra of the photochemical products of bis(cyclopentadienyl)dicarbonyl titanium, TiCp2(CO)(2), isolated in an Ar matrix and a N-2 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)(N-2), TiCp2(N-2), and TiCp2(N-2)(2) were produced in the N-2 matrix. The yields of the species changed with the duration of UV-irradiation. Annealing of the sample resulted in the disappearance of unstable TiCp2(N-2) and an increase of TiCp2(N-2)(2). Isotope shifts of the infrared spectra were measured using N-15(2) 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. (C) 2019 Elsevier B.V. All rights reserved.