Synthesis and thermal and hydrolytic conversion of heterometallic copper oxide-alkoxides
- Indiana Univ., Bloomington, IN (United States)
The synthesis, characterization, thermal decomposition, and full hydrolysis of Cu{sup I}{sub 2}Zr{sub 2}(O{sup i}Pr){sub 10} (1), Cu{sup I}{sub 4}Zr{sub 4}O(O{sup i}-Pr){sub 18}(2), and Cu{sup II}{sub 4}Zr{sub 4}O{sub 3}(O{sup i}Pr){sub 18}(3) are reported. Compound 1 is converted to compound 2 via hydrolysis. Species 1 and 2 are converted to 3 via oxidation with dioxygen. The molecular structure for 2 consists of two [Cu{sub 2}({mu}{sub 2}-OR){sub 2}Zr{sub 2}Zr{sub 2}({mu}{sub 2}-OR){sub 3}(OR){sub 4}]{sup +} fragments bound together via a pseudoterahedron {mu}{sub 4}-O{sup 2{minus}} ligand bridging the copper centers. The X-ray structure of 3 consists of a planar Cu{sub 4}O(O{sup i}Pr){sub 2}{sup 4+} fragment capped by two Zr{sub 2}O(O{sup i}Pr){sub 8}{sup 2{minus}} face-sharing bioctahedral units. The central oxo of the copper fragment is rigorously square-planar. Magnetic studies of 3 reveal a singlet ground state both in solution and the solid state. TGA studies of 1-3 reveal that all the systems undergo internal redox, producing copper metal, acetone, and H{sub 2}. The final products contained an increasing amount of zirconia with increasing number f oxo ligands in the precursor species. Full hydrolysis of 1 and 3, followed by thermolysis, produced Cu{sup o}, Cu{sub 2}O, and CuO with zirconia depending on thermolysis conditions. Results also indicate that precursor design influences the thermolysis behavior of the solid-state product.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 450855
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 10 Vol. 33; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
Similar Records
Copper-zirconium alkoxides: Metal oxidation state and ligand effects on the conversion to solid-state materials
A planar oxocuprate(II) array via heterometallic alkoxide chemistry
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]
Conference
·
Thu Dec 30 23:00:00 EST 1993
·
OSTI ID:141009
A planar oxocuprate(II) array via heterometallic alkoxide chemistry
Journal Article
·
Tue Dec 18 23:00:00 EST 1990
· Journal of the American Chemical Society; (United States)
·
OSTI ID:5737767
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
·
Tue Mar 30 23:00:00 EST 1993
· Inorganic Chemistry; (United States)
·
OSTI ID:6208822