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Title: Synthesis of arene-soluble mixed-metal Zr/Ce, Zr/Y, and related {l_brace}[Zr{sub 2}(O{sup i}Pr){sub 9}]LnX{sub 2}{r_brace}{sub n} complexes using the dizirconium nonaisopropoxide ligand

Journal Article · · Inorganic Chemistry
DOI:https://doi.org/10.1021/ic991272+· OSTI ID:20075875

The utility of polydentate monoanionic [Zr{sub 2}(O{sup i}Pr){sub 9}]{sup {minus}} in generating arene-soluble, unsolvated, mixed-metal Zr/Ce and Zr/Y complexes is described. The synthesis of other mixed-metal zirconium lanthanide complexes was also studied to explore the relationship of metal size to structure. Lanthanide trihalides react in THF with KZr{sub 2}(O{sup i}Pr){sub 9} to form unsolvated dimers, {l_brace}[Zr{sub 2}(O{sup i}Pr){sub 9}][LnCl{sub 2}{r_brace}{sub 2}], with the larger metals, Ln = Ce (1), Ho (2), Y (3), and unsolvated monomers, [Zr{sub 2}(O{sup i}Pr){sub 9}]LnCl{sub 2}, with the smaller elements, Ln = Er (4), Yb (5). The synthesis of a monomeric iodide analogue, [Zr{sub 2}(O{sup i}Pr){sub 9}]TmI{sub 2}, 6, by reduction of Zr{sub 2}(O{sup i}Pr){sub 8}({sup i}PrOH){sub 2} with TmI{sub 2}(DME){sub 3} is also reported. In all of these complexes, the [Zr{sub 2}(O{sup i}Pr){sub 9}]{sup {minus}} subunit is tetradentate. 1--6 are compared with related cyclopentadienyl halide complexes to evaluate the special features of the dizirconium nonaisopropoxide ligand versus cyclopentadienide.

Research Organization:
Univ. of California, Irvine, CA (US)
OSTI ID:
20075875
Journal Information:
Inorganic Chemistry, Vol. 39, Issue 10; Other Information: PBD: 15 May 2000; ISSN 0020-1669
Country of Publication:
United States
Language:
English