Assembly of 3-D network structures containing oxydiacetate and CeIII or CeIV

Behrsing, Thomas, Deacon, Glen B., Forsyth, Craig M., Forsyth, Maria, Skelton, Brian W. and White, Allan H. 2003, Assembly of 3-D network structures containing oxydiacetate and CeIII or CeIV, Zeitschrift für anorganische und allgemeine chemie, vol. 629, no. 1, pp. 35-44, doi: 10.1002/zaac.200390014.

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Title Assembly of 3-D network structures containing oxydiacetate and CeIII or CeIV
Formatted title Assembly of 3-D network structures containing oxydiacetate and CeIII or CeIV
Author(s) Behrsing, Thomas
Deacon, Glen B.
Forsyth, Craig M.
Forsyth, MariaORCID iD for Forsyth, Maria
Skelton, Brian W.
White, Allan H.
Journal name Zeitschrift für anorganische und allgemeine chemie
Volume number 629
Issue number 1
Start page 35
End page 44
Publisher Wiley Interscience
Place of publication Malden, MA.
Publication date 2003-01
ISSN 0044-2313
Keyword(s) cerium
carboxylate ligands
crystal structure
Summary Reaction of CeCl3·7H2O with Na2(oda) (oda = O(CH2CO2)22— oxydiacetate) in a 2:3 ratio gives the neutral cerium(III) complex [Ce2(oda)3(H2O)3]·9H2O (1). Treatment of a 1:3 mixture of CeCl3·7H2O and H2oda in water with 4 molar equivalents of NaOH also gives 1 but, with a larger excess of NaOH, the tri-sodium salt Na3[Ce(oda)3]·9H2O (2) is isolated. Formation of a tri-ammonium analogue of 2 can be achieved by neutralisation of an aqueous solution of CeCl3·7H2O and H2(oda) in a 1:3 ratio by NH4OH, giving (NH4)3[Ce(oda)3]·7H2O (3). Use of the cerium(IV) reagent (NH4)2[Ce(NO3)6] with Na2(oda) results in reduction to cerium(III) under ambient conditions and isolation of 1. However, in the absence of light this reaction yields crystals of the novel cerium(IV) heterobimetallic [Ce(oda)3Na4(NO3)2] (4). Each of these complexes exhibit a 3-D network structure having a common nine-coordinate [Ce(oda)3]n— (n = 2 or 3) subunit, irrespective of the oxidation state of cerium. In 1, six [Ce(oda)3]3— anions are connected, through bridging bidentate carboxylates, to a second Ce3+ site further coordinated by three water molecules. In contrast, the ammonium salt 2, displays isolated [Ce(oda)3]3— anions, devoid of further carboxylate bonding, but enmeshed within a network of hydrogen-bonded NH4+ cations and water molecules. The remarkable structure of 4 consists of infinite 2-D sheets of [Na2(NO3)]+ pillared by [Ce(oda)3]2— units, the connectivity arising by multidentate nitrate and carboxylate bridging.
Language eng
DOI 10.1002/zaac.200390014
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, WILEY-VCH Verlag GmbH & Co. KGaA
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