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Synthesis of Arene-Soluble Mixed-Metal Zr/Ce, Zr/Y, and Related {[Zr2(OiPr)9]LnX2}n Complexes Using the Dizirconium Nonaisopropoxide Ligand

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journal contribution
posted on 20.04.2000, 00:00 by William J. Evans, Matthew A. Johnston, Michael A. Greci, Mohammad A. Ansari, Jason C. Brady, Joseph W. Ziller
The utility of polydentate monoanionic [Zr2(OiPr)9]- 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 KZr2(OiPr)9 to form unsolvated dimers, {[Zr2(OiPr)9]LnCl2}2, with the larger metals, Ln = Ce (1), Ho (2), Y (3), and unsolvated monomers, [Zr2(OiPr)9]LnCl2, with the smaller elements, Ln = Er (4), Yb (5). The synthesis of a monomeric iodide analogue, [Zr2(OiPr)9]TmI2, 6, by reduction of Zr2(OiPr)8(iPrOH)2 with TmI2(DME)3 is also reported. In all of these complexes, the [Zr2(OiPr)9]- subunit is tetradentate. 16 are compared with related cyclopentadienyl halide complexes to evaluate the special features of the dizirconium nonaisopropoxide ligand versus cyclopentadienide.