Interconvertible Side-On- and End-On-Bonded Oxo−Superoxo Titanium Ozonide Complexes

Abstract

This report presents the preparation and characterization of two interconvertible titanium ozonide complexes using matrix-isolation infrared spectroscopy and density functional theory calculations (B3LYP/6-311+G(d)). The titanium atoms react with O2 to form primarily the inserted TiO2 molecules in solid argon, which further react with O2 to form OTi(eta2-O2)(eta2-O3) via a weakly bonded TiO2(O2)2 intermediate. The OTi(eta2-O2)(eta2-O3) complex is characterized as [(TiO)2+(O2-)(O3-)], that is, a side-on-bonded oxo-superoxo titanium ozonide complex. The side-on-bonded complex rearranges to a less stable end-on-bonded OTi(eta2-O2)(eta1-O3) isomer under 532 nm laser irradiation, while the reverse reaction (end-on to side-on) proceeds upon sample annealing.