IR SPECTROSCOPIC STUDY OF LANTHANIDE HYDROXOCOMPLEXES WITH ESTERS OF ACETOACETIC ACID
Abstract
The IR spectra of hydroxo complexes of lanthanides (Ln) with β-ketoesters methyl, ethyl, and allyl acetoacetate having the general formula LnL2OH·H2O (Ln = La, Gd, Lu; L - β-ketoesterate anion) were studied in the 400-1700 cm- 1 range. In order to interpret the spectra and assign bands caused by vibrations of the β-ketoesterate ligands, a normal coordinate analysis of the model complexes LnL(OH)2 (Ln = La, Lu) was performed at the approximation of PBE0/ECP46(60)MWB+DZP. The experimental data coupled with theoretical calculations show that the radius of the Ln(III) ion and the structure of the hydrocarbon radical of the alkoxy substituent have a negligible effect on the value of π-electron delocalization in the [OCCCO] conjugated system of the chelate fragments, whereas the decrease of the Ln(III) ionic radius leads to increase of conjugation in the esteric C(O)O group of ligands.
About the Authors
A. M. Mishchenko
V. I. Vernadsky Institute of General and Inorganic Chemistry of the National Academy of Sciences of Ukraine
Russian Federation
Russian Federation
E. K. Trunova
V. I. Vernadsky Institute of General and Inorganic Chemistry of the National Academy of Sciences of Ukraine
Russian Federation
Russian Federation
L. I. Zheleznova
V. I. Vernadsky Institute of General and Inorganic Chemistry of the National Academy of Sciences of Ukraine
Russian Federation
Russian Federation
T. A. Makotryk
V. I. Vernadsky Institute of General and Inorganic Chemistry of the National Academy of Sciences of Ukraine
Russian Federation
Russian Federation
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Review
For citations:
Mishchenko A.M., Trunova E.K., Zheleznova L.I., Makotryk T.A. IR SPECTROSCOPIC STUDY OF LANTHANIDE HYDROXOCOMPLEXES WITH ESTERS OF ACETOACETIC ACID. Zhurnal Prikladnoii Spektroskopii. 2019;86(2):188-194. (In Russ.)
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