Primary steps in the hydrolyses of two heterometallic alkoxides. Characterization of [LiTiO(O[sup i]Pr)[sub 3]][sub 4] and BaZr[sub 4](OH)(O[sup i]Pr)[sub 17]

Journal Article · Wed Mar 31 04:00:00 EST 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00059a040· OSTI ID:6208822

Kuhlman, R; Streib, W E; Huffman, J C; Caulton, K G ^[1]; Vaartstra, B A ^[2]

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1. Indiana Univ., Bloomington (United States)
2. Advanced Technology Materials, Inc., Danbury, CT (United States)

Partial hydrolysis of [LiTi(O[sup i]Pr)[sub 5]][sub 2] yields a tetrameric oxo-alkoxide, [LiTiO(O[sup i]Pr)[sub 3]][sub 4]. The compound has been characterized in solution by [sup 1]H and [sup 13]C NMR spectroscopy and in the solid state by X-ray crystallography. The molecule crystallizes in the space group C2/c with a = 18.460(3) [Angstrom], b = 17.904(3) [Angstrom], c = 15.832(2) [Angstrom], [beta] = 90.11(0)[degrees], and Z = 4. Titanium and oxo atoms are located in a middle layer with Li atoms in layers above and below, supported by alkoxide bridges. The similarity to ferroelectric titanates is evident in the coordination sphere of Ti in [LiTiO(O[sup i]Pr)[sub 3]][sub 4]. Addition of 1 equiv of water to BaZr[sub 4](O[sup i]Pr)[sub 18] in THF yields the hydroxide BaZr[sub 4](OH)(O[sup i]Pr)[sub 17] in a simple acid/base ligand exchange reaction. Characterization by X-ray diffraction shows that the molecule crystallizes in the C2/c space group, with dimensions a = 58.735(12) [Angstrom], b = 12.555(13) [Angstrom], c = 19.321(4) [Angstrom], and [beta] = 94.17(1)[degrees] (Z = 8). Variable-temperature [sup 1]H and [sup 13]C NMR data are also reported, revealing ligand site exchange local to BaZr[sub 2] triangles. The hydroxide ligand adopts a [mu][sub 3]-site, bridging the barium and two zirconium atoms. In both cases, the metal stoichiometry has been retained in the final product. 13 refs., 2 figs., 5 tabs.

• OSTI ID: 6208822
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:7; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKALI METAL COMPOUNDS
ALKALINE EARTH METAL COMPOUNDS
ALKOXIDES
BARIUM COMPOUNDS
CHALCOGENIDES
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DECOMPOSITION
DIFFRACTION
HYDROGEN COMPOUNDS
HYDROLYSIS
HYDROXIDES
LATTICE PARAMETERS
LITHIUM COMPOUNDS
LYSIS
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
OXIDES
OXYGEN COMPOUNDS
RESONANCE
SCATTERING
SOLVOLYSIS
STOICHIOMETRY
TITANIUM COMPLEXES
TITANIUM COMPOUNDS
TITANIUM OXIDES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION
ZIRCONIUM COMPOUNDS
ZIRCONIUM HYDROXIDES