Wydział Chemii

Rafał M. Petrus

Anna Drąg-Jarząbek

Józef Utko

Dominik Bykowski

Tadeusz Lis

Piotr Sobota

2017

Inorganic Chemistry

56

11365-11374

10.1021/acs.inorgchem.7b01772

Naukowa

Angielski

Artykuł

The effect of alkaline-earth-metal alkoxides on the protonolysis of Cp₂M′Cl₂ (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 [M₂M′₂(μ₃-OEt)₂(μ-OEt)₄(OEt)₆(EtOH)₄] with M = Mg and M′ = Ti (1), Zr (2), and Hf (3), [Ca₆Ti₄(μ₆-O)₂(μ₄-O)₂(μ₃-OEt)₁₂(OEt)₁₂(EtOH)₆Cl₄] (4), and [M₂M′₂(μ₄-O)(μ-OEt)₅(OEt)₄(EtOH)₄Cl]_n with M = Ca and M′ = Zr (5) and Hf (6) were prepared via elimination of the cyclopentadienyl ring from Cp₂M′Cl₂ as CpH in the presence of M(OEt)₂ and ethanol (EtOH) as a source of protons. Meanwhile, similar reactions involving the initial substitution of Cl ligands by OEt groups in Cp₂M′Cl₂ (M′ = Ti, Zr, Hf) resulted in the formation of [M₂M′₂(μ₃-OEt)₂(μ-OEt)₄(OEt)₆(EtOH)₄] 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 MgTiO₃ along with small amounts of Mg₂TiO₄, Mg₂Zr₅O₁₂, or Mg₂Hf₅O₁₂ binary metal oxides. The thermolysis of calcium compounds 4 and 7–9 led to highly pure CaTiO₃, CaZrO₃, or CaHfO₃ perovskite-like oxide particles with diameters of 20–30 nm.

http://dx.doi.org/10.1021/acs.inorgchem.7b01772

https://www.acs.org/content/acs/en.html