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NMR and IR Spectroscopic Examination of the Hydrolytic Stability of Organic Ligands in Metal Alkoxide Complexes and of Oxygen Bridged Heterometal Bonds

Published online by Cambridge University Press:  10 February 2011

D. Hoebbel ,
T. Reinert  and
H. Schmidt
D. Hoebbel
Affiliation:
Institut für Neue Materialien, Im Stadtwald, Geb. 43, D-66123 Saarbrücken, Germany
T. Reinert
Affiliation:
Institut für Neue Materialien, Im Stadtwald, Geb. 43, D-66123 Saarbrücken, Germany
H. Schmidt
Affiliation:
Institut für Neue Materialien, Im Stadtwald, Geb. 43, D-66123 Saarbrücken, Germany
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Abstract

IR and 13C NMR investigations of the hydrolytic stabilities of the saturated and unsaturated ß-keto ligands acetylacetone (ACAC), ethylacetoacetate (EAA), allylacetoacetate (AAA), methacryloxyethyl-acetoacetate (MEAA) of the Al-, Ti- and Zr-butoxide complexes show a strong dependence on the type of the metal alkoxide and the structure of the organic ligands. The hydrolytic stabilities of the ligands decrease in the order Al->Zr->Ti-alkoxide and ACAC>AAA>EAA≥MEAA. Sol-gel reactions of complexes having a weak ligand stability leads to a larger water consumption and to larger particle sizes in sols than those with stable ACAC ligands. Heterometal bonds, i.e. Si-O-Al, Si-O-Ti and Si-O-Zr, in the system diphenylsiloxanediol/ metal alkoxide (complex) proved by 29Si and 17O NMR are hydrolysed to a different extent depending on the water amount, the type of the Si-O-M bond and the structure of the heterometal species. The degradation of the heterometal bonds leads to a separation of MO-M and Si-O-Si bonds which can entail a decreased homogeneity of the materials at a molecular level.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 435: Symposium V – Better Ceramics Through Chemistry VII , 1996 , 461
Copyright
Copyright © Materials Research Society 1996

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