Interconvertible side-on- and end-on-bonded oxo-superoxo titanium ozonide complexes

Area of Science:

• Inorganic Chemistry
• Quantum Chemistry
• Spectroscopy

Background:

• Titanium oxides are crucial in catalysis and materials science.
• Ozonide complexes are rare and their synthesis and characterization are of significant interest.

Purpose of the Study:

• To synthesize and characterize novel titanium ozonide complexes.
• To investigate the interconversion between different isomers of titanium ozonide complexes.
• To elucidate the bonding and electronic structure of these complexes.

Main Methods:

• Matrix-isolation infrared spectroscopy was employed for characterization.
• Density functional theory (DFT) calculations using the B3LYP/6-311+G(d) method were performed.
• Laser irradiation and sample annealing were used to induce and study isomer interconversion.

Main Results:

• Two interconvertible titanium ozonide complexes, OTi(eta2-O2)(eta2-O3) and OTi(eta2-O2)(eta1-O3), were successfully prepared and characterized.
• The side-on-bonded complex OTi(eta2-O2)(eta2-O3) was identified as a stable oxo-superoxo titanium ozonide, [(TiO)2+(O2-)(O3-)].
• The side-on isomer rearranges to a less stable end-on isomer under laser irradiation, with the reverse reaction occurring upon annealing.

Conclusions:

• The study successfully synthesized and characterized two novel titanium ozonide complexes.
• The interconversion between side-on and end-on bonded isomers was demonstrated, providing insights into their stability and reactivity.
• The findings contribute to the understanding of titanium-oxygen chemistry and the nature of ozonide complexes.