Yang Rui, Gong Yu, Zhou Han, Zhou Mingfei
Department of Chemistry & Laser Chemistry Institute, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai 200433, People's Republic of China.
J Phys Chem A. 2007 Jan 11;111(1):64-70. doi: 10.1021/jp0662000.
Reactions of rhodium atoms with dioxygen molecules in solid argon have been investigated using matrix isolation infrared absorption spectroscopy. The rhodium-dioxygen complexes, Rh(eta2-O2), Rh(eta2-O2)2, and Rh(eta2-O2)2(eta1-OO), are produced spontaneously on annealing. The Rh(eta2-O2) complex rearranges to the inserted RhO2 molecule under visible light irradiation. Experiments doped with xenon in argon show that the rhodium-dioxygen complexes are coordinated by one or two noble gas atoms in solid noble gas matrixes. Hence, the Rh(eta2-O2), Rh(eta2-O2)2, and Rh(eta2-O2)2(eta1-OO) molecules trapped in solid noble gas matrixes should be regarded as the Rh(eta2-O2)(Ng)2, Rh(eta2-O2)2(Ng)2, and Rh(eta2-O2)2(eta1-OO)(Ng) (Ng = Ar or Xe) complexes. The product absorptions are identified on the basis of isotopic substitution and density functional theory calculations.
利用基质隔离红外吸收光谱法研究了固态氩中铑原子与双氧分子的反应。铑-双氧配合物Rh(η²-O₂)、Rh(η²-O₂)₂和Rh(η²-O₂)₂(η¹-OO)在退火时自发产生。Rh(η²-O₂)配合物在可见光照射下重排为插入式的RhO₂分子。在氩气中掺杂氙的实验表明，铑-双氧配合物在固态稀有气体基质中由一个或两个稀有气体原子配位。因此，被困在固态稀有气体基质中的Rh(η²-O₂)、Rh(η²-O₂)₂和Rh(η²-O₂)₂(η¹-OO)分子应被视为Rh(η²-O₂)(Ng)₂、Rh(η²-O₂)₂(Ng)₂和Rh(η²-O₂)₂(η¹-OO)(Ng)（Ng = Ar或Xe）配合物。根据同位素取代和密度泛函理论计算确定了产物吸收峰。
