Petrus Rafał, Drąg-Jarząbek Anna, Utko Józef, Bykowski Dominik, Lis Tadeusz, Sobota Piotr
Faculty of Chemistry, University of Wrocław , 14 F. Joliot-Curie, 50-383 Wrocław, Poland.
Faculty of Chemistry, Wrocław University of Science and Technology , 23 Smoluchowskiego, 50-370 Wrocław, Poland.
Inorg Chem. 2017 Sep 18;56(18):11365-11374. doi: 10.1021/acs.inorgchem.7b01772. Epub 2017 Sep 6.
The effect of alkaline-earth-metal alkoxides on the protonolysis of CpM'Cl (M' = Ti, Zr, Hf; Cp = cyclopentadiene) was investigated. This approach enabled the design of compounds with well-defined molecular structures to generate high-purity binary metal oxides. Single-source molecular precursors with structures of [MM'(μ-OEt)(μ-OEt)(OEt)(EtOH)] with M = Mg and M' = Ti (1), Zr (2), and Hf (3), [CaTi(μ-O)(μ-O)(μ-OEt)(OEt)(EtOH)Cl] (4), and [MM'(μ-O)(μ-OEt)(OEt)(EtOH)Cl] with M = Ca and M' = Zr (5) and Hf (6) were prepared via elimination of the cyclopentadienyl ring from CpM'Cl as CpH in the presence of M(OEt) and ethanol (EtOH) as a source of protons. Meanwhile, similar reactions involving the initial substitution of Cl ligands by OEt groups in CpM'Cl (M' = Ti, Zr, Hf) resulted in the formation of [MM'(μ-OEt)(μ-OEt)(OEt)(EtOH)] with M = Ca and M' = Ti (7), Zr (8), and Hf (9). The precursors were characterized by elemental analysis, NMR spectroscopy, and single-crystal X-ray structural analysis. Magnesium compounds 1-3 decomposed at 750-850 °C to give MgTiO along with small amounts of MgTiO, MgZrO, or MgHfO binary metal oxides. The thermolysis of calcium compounds 4 and 7-9 led to highly pure CaTiO, CaZrO, or CaHfO perovskite-like oxide particles with diameters of 20-30 nm.
研究了碱土金属醇盐对CpM'Cl（M' = Ti、Zr、Hf；Cp = 环戊二烯）质子解的影响。这种方法能够设计出具有明确分子结构的化合物，以生成高纯度的二元金属氧化物。通过在M(OEt)和作为质子源的乙醇（EtOH）存在下，从CpM'Cl中消除环戊二烯基环作为CpH，制备了结构为[MM'(μ-OEt)(μ-OEt)(OEt)(EtOH)]（M = Mg且M' = Ti（1）、Zr（2）和Hf（3））、[CaTi(μ-O)(μ-O)(μ-OEt)(OEt)(EtOH)Cl]（4）以及[MM'(μ-O)(μ-OEt)(OEt)(EtOH)Cl]（M = Ca且M' = Zr（5）和Hf（6））的单源分子前驱体。同时，涉及在CpM'Cl（M' = Ti、Zr、Hf）中用OEt基团初始取代Cl配体的类似反应，导致形成了M = Ca且M' = Ti（7）、Zr（8）和Hf（9）的[MM'(μ-OEt)(μ-OEt)(OEt)(EtOH)]。通过元素分析、核磁共振光谱和单晶X射线结构分析对前驱体进行了表征。镁化合物1 - 3在750 - 850℃分解，生成MgTiO以及少量的MgTiO、MgZrO或MgHfO二元金属氧化物。钙化合物4和7 - 9的热解产生了直径为20 - 30 nm的高纯度钙钛矿型CaTiO、CaZrO或CaHfO氧化物颗粒。
