Gong Yu, Zhou Mingfei, Tian Shan Xi, Yang Jinlong
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Advanced Materials Laboratory, Fudan University, Shanghai 200433, People's Republic of China.
J Phys Chem A. 2007 Jul 19;111(28):6127-30. doi: 10.1021/jp074097o. Epub 2007 Jun 20.
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.
本报告介绍了使用基质隔离红外光谱和密度泛函理论计算（B3LYP/6-311+G(d)）制备和表征两种可相互转化的臭氧钛配合物。钛原子与O₂反应，在固态氩中主要形成插入式TiO₂分子，这些分子进一步与O₂反应，通过弱键合的TiO₂(O₂)₂中间体形成OTi(η²-O₂)(η²-O₃)。OTi(η²-O₂)(η²-O₃)配合物的特征为[(TiO)²⁺(O₂⁻)(O₃⁻)]，即一种侧基键合的氧代超氧臭氧钛配合物。在532 nm激光照射下，侧基键合的配合物重排为稳定性较低的端基键合OTi(η²-O₂)(η¹-O₃)异构体，而在样品退火时发生逆反应（从端基到侧基）。
