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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

Abstract

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.

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Univ. of California, Irvine, CA (US)
OSTI Identifier:
20075875
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 39; Journal Issue: 10; Other Information: PBD: 15 May 2000; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; SYNTHESIS; CRYSTAL STRUCTURE; ZIRCONIUM COMPLEXES; RARE EARTH COMPLEXES; ISOPROPYL RADICALS; AROMATICS; SOLUBILITY

Citation Formats

Evans, W.J., Johnston, M.A., Greci, M.A., Ansari, M.A., Brady, J.C., and Ziller, J.W. 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. United States: N. p., 2000. Web. doi:10.1021/ic991272+.
Evans, W.J., Johnston, M.A., Greci, M.A., Ansari, M.A., Brady, J.C., & Ziller, J.W. 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. United States. doi:10.1021/ic991272+.
Evans, W.J., Johnston, M.A., Greci, M.A., Ansari, M.A., Brady, J.C., and Ziller, J.W. Mon . "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". United States. doi:10.1021/ic991272+.
@article{osti_20075875,
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},
author = {Evans, W.J. and Johnston, M.A. and Greci, M.A. and Ansari, M.A. and Brady, J.C. and Ziller, J.W.},
abstractNote = {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.},
doi = {10.1021/ic991272+},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 10,
volume = 39,
place = {United States},
year = {2000},
month = {5}
}