Synthesis and structure of novel group IV tridentate alkoxide complexes and ceramic thin films derived therefrom. X-ray structures of (H{sub 3}CC(CH{sub 2}-{mu}{sub 3}-O)(CH{sub 2}-{mu}-O){sub 2}){sub 2}Ti{sub 4}(OCH(CH{sub 3}){sub 2}){sub 10}, (H{sub 3}CCH{sub 2}C(CH{sub 2}-{mu}{sub 3}-O)(CH{sub 2}-{mu}-O){sub 2}){sub 2}Ti{sub 4}(OCH(CH{sub 3}){sub 2}){sub 10}, and (H{sub 3}CC(CH{sub 2}-{mu}-O){sub 3}){sub 2}Zr{sub 4}({mu}-OCH(CH{sub 3}){sub 2}){sub 2}(OCH(CH{sub 3}){sub 2}){sub 8}
- Sandia National Lab., Albuquerque, NM (United States)
- Univ. of California, Irvine, CA (United States)
An alcoholysis exchange between tris(hydroxymethyl)ethane (THME-H{sub 3}) or tris(hydroxymethyl)propane (THMP-H{sub 3}) and group IV metal isopropoxides yields compounds of the general formula (THMR){sub 2}M{sub 4}(OCHMe{sub 2}){sub 10}[M = Ti (R = E, 1; P, 2); Zr (R = E, 3; P, 4)]. 1 and 2 are formed in toluene, at ambient glovebox temperatures, and adopt a typical fused-M{sub 3}O{sub 12} structure where each titanium atom is surrounded by six oxygens in a slightly distorted face-shared bioctahedral arrangement. All of the oxygens of the central core are from the THMR ligand, present as {mu}-O and {mu}{sub 3}-O oxygen bridges. Generation of 3 or 4 requires heating in toluene at reflux temperatures. The zirconium atoms of 3 possess an extremely distorted edge-shared bioctahedral geometry where the central core consists of a Zr{sub 4}O{sub 8} ring (eight oxygens: six from THME ligands and two from isopropoxide ligands). Each of the zirconium atoms is six-coordinated with four bridging oxygens and two terminal isopropoxide ligands. Spincast deposited films generated from toluene solutions of 1 and 3 indicate that increased uniformity of the films and decreased hydrolysis occur in comparison to the cases of Ti(OCHMe{sub 2}){sub 4}, 5, and [Zr(OCHMe{sub 2}){sub 4}{center_dot}HOCHMe{sub 2}]{sub 2}, 6, respectively.
- Research Organization:
- Sandia National Laboratory
- DOE Contract Number:
- AC04-94AL85000
- OSTI ID:
- 457088
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 5 Vol. 34; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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