Cerium acetylacetonates—new aspects, including the lamellar clathrate [Ce(acac)4]·10H2O

Behrsing, Thomas, Bond, Alan M., Deacon, Glen B., Forsyth, Craig M., Forsyth, Maria, Kamble, Kalpana J., Skelton, Brian W. and White, Allan H. 2003, Cerium acetylacetonates—new aspects, including the lamellar clathrate [Ce(acac)4]·10H2O, Inorganica chimica acta, vol. 352, pp. 229-327.

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Title Cerium acetylacetonates—new aspects, including the lamellar clathrate [Ce(acac)4]·10H2O
Formatted title Cerium acetylacetonates—new aspects, including the lamellar clathrate [Ce(acac)4]·10H2O
Author(s) Behrsing, Thomas
Bond, Alan M.
Deacon, Glen B.
Forsyth, Craig M.
Forsyth, Maria
Kamble, Kalpana J.
Skelton, Brian W.
White, Allan H.
Journal name Inorganica chimica acta
Volume number 352
Start page 229
End page 327
Publisher Elsevier
Place of publication Amsterdam, The Netherlands
Publication date 2003-08-06
ISSN 0020-1693
1873-3255
Keyword(s) CeIII/IV
acac
structures
electrochemistry
redox
Summary Reactions of CeCl3·7H2O and Ce(NO3)3·6H2O with Naacac or NH4acac in aqueous solution at 21 and 45 °C yielded the trihydrate [Ce(acac)3(H2O)2]·H2O and the dihydrate [Ce(acac)3(H2O)2], respectively, whereas similar treatment of (NH4)2[Ce(NO3)6] gave the trihydrate at both temperatures. Desiccation of the hydrates over silica gel left the dihydrate unchanged, whereas the trihydrate underwent decomposition rather than dehydration. Aerial oxidation of [Ce(acac)3(H2O)2] in CH2Cl2 and toluene yielded α-[Ce(acac)4] and β-[Ce(acac)4], respectively, the structure of the former being re-determined with improved precision. Careful treatment of aqueous (NH4)4[Ce(SO4)4] and Hacac (initially pH 1–2) with aqueous ammonia to pH 5 precipitated hydrated [Ce(acac)4], from which [Ce(acac)4]·10H2O was isolated as unstable, light-sensitive single crystals, and the structure was determined. The complex is a laminar clathrate containing layers of Ce(acac)4 molecules sandwiched between extensive hydrogen-bonded layers of water molecules which do not interact with the metal. Electrochemical experiments confirmed the unstable nature of hydrated CeIII(acac)3, while the reduction of [Ce(acac)4] yielded well-defined cyclic voltammograms in acetonitrile and acetone, corresponding to a quasi-reversible process. For the [CeIV(acac)4]/[CeIII(acac)4]redox couple, a calculated reversible potential of 0.22±0.02 V versus SHE was obtained in acetone or acetonitrile (0.1 M Bu4NPF6) at both gold and glassy carbon electrodes. This potential is consistent with the ease of both oxidation and reduction of cerium acetylacetonate complexes as found in the synthetic studies.
Language eng
Field of Research 039999 Chemical Sciences not elsewhere classified
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1.1 Refereed article in a scholarly journal
Copyright notice ©2003, Elsevier Science B.V.
Persistent URL http://hdl.handle.net/10536/DRO/DU:30030059

Document type: Journal Article
Collection: Institute for Technology Research and Innovation
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