Gong Yu, Zhou Mingfei
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Advanced Materials Laboratory, Fudan University, Shanghai 200433, P. R. China.
J Phys Chem A. 2008 Oct 30;112(43):10838-42. doi: 10.1021/jp806442y. Epub 2008 Oct 2.
Two FeO 3 isomers were prepared and characterized using matrix isolation infrared spectroscopy and theoretical calculations. The iron monoxide molecules produced from laser evaporation of the bulk iron oxide target react with dioxygen in solid argon to form the (eta (2)-O 2)FeO complex spontaneously on annealing. The (eta (2)-O 2)FeO complex was predicted to have a (5)B 2 ground state with a planar C 2 v structure, in which the O 2 fragment is side-on bonded to the iron center. The (eta (2)-O 2)FeO complex rearranges to the more stable iron trioxide isomer upon visible light (lambda > 500 nm) irradiation. The iron trioxide molecule was predicted to have a closed-shell singlet ground state with a planar D 3 h symmetry, in which the iron possesses a +6 oxidation state.
制备了两种FeO₃异构体，并使用基质隔离红外光谱和理论计算对其进行了表征。通过对块状氧化铁靶材进行激光蒸发产生的一氧化铁分子在固体氩气中与氧气反应，在退火时自发形成(η² - O₂)FeO配合物。预测(η² - O₂)FeO配合物具有平面C₂ᵥ结构的(⁵)B₂基态，其中O₂片段以侧基方式键合到铁中心。在可见光（λ > 500 nm）照射下，(η² - O₂)FeO配合物重排为更稳定的三氧化二铁异构体。预测三氧化二铁分子具有平面D₃ₕ对称性的闭壳单重基态，其中铁具有 +6氧化态。
