Transformation of molecular compounds with Ba(Sr)/Al/Si and Ca(Sr, Ba)/Ti(Zr, Hf)/Si heteroelements as new efficient route to metal silicate materials.

Silicon-based moieties were anchored in heterometallic alkoxide platforms to obtain molecular clusters based on the M-O-M'-O-Si motif for the generation of mixed-metal silicate materials. Single-source molecular precursors with structures [M{(μ-ddbfo)2Al(OSiPh3)2}2], where dbbfoH = 2,3-dihydro-2,2-dimethylbenzofuran-7-ol and M = Ba (1), Sr (2), [Sr4Ti2(μ6-O)(μ3,η2-OCH2CH2OMe)8(η-OCH2CH2OMe)2(OSiPh3)4] (3), [Sr4M'2(μ4-OH)(μ3,η2-OCH2CH2OMe)4(μ,η2-OCH2CH2OMe)6(μ-X)(OSiPh3)4] (4, with M' = Zr and X = Cl; 5 with M' = Hf and X = OH), [Sr3Hf2(μ5-O)(μ3,η2-OCH2CH2OMe)4(OCH2CH2OMe)4(OSiPh3)4] (6), and [Ca2M'2(μ3-OH)2(μ,η2-OCH2CH2OMe)4(η2-HOCH2CH2OMe)2(η-OCH2CH2OMe)2(OSiPh3)4] for M' = Zr (7), Hf (8), were prepared by substitution of methyl groups, using Ph3SiOH or chloride atoms with KOSiPh3, in [M{(μ-ddbfo)2AlMe2}2] (M = Sr, Ba) or [M4M'2(μ6-O)(μ3,η2-OCH2CH2OMe)8(OCH2CH2OMe)2(HOCH2CH2OMe)xCl4] (M = Ca, Sr, Ba, M' = Ti, Zr, Hf and x = 0, 4). The precursors were characterized by elemental analysis, NMR spectroscopy, and single-crystal X-ray structural analysis.

Molecular Routes to Group IV Magnesium and Calcium Nanocrystalline Ceramics.

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.

Synthesis of Aluminosilicates Containing a Ba(Sr)-O-Al-O-Si Arrangement of Natural Feldspar Mineral.

We report a facile route to multicomponent complexes of [M{(μ-ddbfo)Al(OSiR)}] (M = Ba, Sr; ddbfoH = 2,3-dihydro-2,2-dimethylbenzofuran-7-ol; R = Ph, OBu) as new efficient single-source routes to barium and strontium celsian feldspar Ba(Sr)AlSiO. The resulting complexes were characterized by elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray diffraction. These compounds calcined at 1100 °C to give porous material Ba(Sr)AlSiO·2SiO as an amorphous silica matrix containing spherical oxide nanocrystals of celsian feldspar of ca.

Unexpected Reactions between Ziegler-Natta Catalyst Components and Structural Characterization of Resulting Intermediates.

In this work, we investigated precursors and procatalysts with well-defined crystal structures and morphologies in Ziegler-Natta systems to improve our understanding of the nature of the active metal sites. Molecular cluster precursors such as [Mg4Ti3(μ6-O)(μ3-OH)3(μ-OEt)9(OEt)3(EtOH)3Cl3], [Mg4Ti3(μ6-O)(μ3-OH)(μ3-OEt)2(μ-OEt)9(OEt)3(EtOH)3Cl3], and [Mg6Ti4(μ6-O)2(μ3-OH)4(μ-OEt)14(OEt)4(EtOH)2Cl2] were prepared via simple elimination of the cyclopentadienyl ring from Cp2TiCl2 as CpH in the presence of magnesium metal and ethanol. Titanocene dichloride acts as both a source of titanium and a magnesium-chlorinating agent.

Alkaline Earth Metal Zirconate Perovskites MZrO3 (M=Ba(2+), Sr(2+), Ca(2+)) Derived from Molecular Precursors and Doped with Eu(3+) Ions.

The effect of alkaline earth metal alkoxides on the protonation of zirconocene dichloride was investigated. This approach enabled the design of compounds with preset molecular structures for generating high-purity binary metal oxide perovskites MZrO3 (M=Ba(2+), Sr(2+), Ca(2+)). Single-source molecular precursors [Ba4 Zr2 (μ6 -O)(μ3 ,η(2)-OR)8 (OR)2(η(2) -HOR)2 (HOR)2 Cl4], [Sr4 Zr2 (μ6 -O)(μ3 ,η(2)-OR)8 (OR)2 (HOR)4 Cl4], [Ca4 Zr2 (μ6-O)(μ3 ,η(2)-OR)8 (OR)2 Cl4], and [Ca6 Zr2 (μ2 ,η(2)-OR)12 (μ-Cl)2 (η(2) -HOR)4 Cl6 ]⋅8 CH2 Cl2 were prepared via elimination of the cyclopentadienyl ring from Cp2 ZrCl2 as CpH in the presence of M(OR)2 and alcohol ROH (ROH=CH3OCH2 CH2OH) as a source of protons.