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Issue 2, 1999
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The influence of β-diketones on the induction times for hydrolysis of zirconium(IV) alkoxides

Abstract

The influence of low ligand/Zr mole ratios (ρ=0-0.1) of acetylacetone on the hydrolysis of Zr(OPr n ) 4 has been examined by investigating its effect on the induction time (t i ) before precipitation commences in the system. A remarkable feature of the data is the large increase in the induction time (reduction in hydrolysis/condensation rate) caused by addition of acetylacetone. This occurs even though only a maximum of one in eighty Zr-OR bonds have reacted with ligand and are no longer available for hydrolysis or further condensation. The effects on t i of five other β-diketones having varying steric properties (trifluoroacetylacetone, hexafluoroacetylacetone, benzoylacetone, dibenzoylmethane and dipivaloylmethane) are compared with that of acetylacetone, under similar concentration conditions, with ρ=0.1. Each shows a greater effect than acetylacetone, the largest change being caused by dibenzoylmethane which, under the conditions used, increases the induction time by a factor of 26 relative to acetylacetone. A mechanism rationalising the origin of the effect is discussed.

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Article type: Paper
DOI: 10.1039/A806782A
Citation: J. Mater. Chem., 1999,9, 499-505
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    The influence of β-diketones on the induction times for hydrolysis of zirconium(IV) alkoxides

    M. J. Percy, J. R. Bartlett, J. L. Woolfrey, L. Spiccia and B. O. West, J. Mater. Chem., 1999, 9, 499
    DOI: 10.1039/A806782A

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