A hexanuclear cerium(IV) cluster with mixed coordination environment

Das, Rajorshi; Sarma, Rupam; Baruah, Jubaraj B.

doi:10.1016/j.inoche.2010.03.050

Cited by 55 publications

(31 citation statements)

References 15 publications

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“…It is embedded in a cavity available in the tungsten ribbon by six bonds with oxygen atoms of the ribbon and four bonds with bridging µ 3 ‐O atoms of the hexamer. As far as we know, this hexanuclear core bearing three different coordination spheres is different from those observed in the literature where all six atoms of the cluster are in a square antiprismatic geometry . Due to the low quality of the structure, only one independent sodium cation was localized, giving four related sodium atoms in the molecular compound.…”

Section: Resultscontrasting

confidence: 62%

Influence of the pH on the Condensation of Tetravalent Cerium Cations in Association with [α‐SiW₉O₃₄]^10– Leading to the Formation of a Ce₆O₄(OH)₄ Core

et al. 2016

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The reaction of Na10[α‐SiW9O34] with 4f tetravalent cerium cations in aqueous solution in the presence of sodium acetate at different pH values leads to the stabilization of three cerium‐based polyanionic molecular clusters [Ce3(µ2‐OH)3(µ3‐O)(SiW9O34)2]13– (1), [Ce3(µ2‐O)3(SiW9O34)2]14– (2), and {[Ce6(µ3‐O)4(µ3‐OH)4]2(W8O32)(SiW9O34)4}32– (3). The condensation behavior of cerium in this kind of association with trivacant polyoxometalates (POMs) when a pH variation occurs is relatively unknown and needed to be explored. Compounds 1 and 2 consist of a trinuclear cerium cluster fragment stabilized by two POM moieties with a variation of the central cerium cluster from [Ce3(µ2‐OH)3(µ3‐O)] to [Ce3(µ2‐O)3]. Compound 3 appears much more condensed with two hexanuclear [Ce6(µ3‐O)4(µ3‐OH)4] groups that are stabilized by the SiW9O34 moieties and a W8O32 tungsten ring. This evolution in cluster size and composition reflects the pH variation applied during their synthesis. The molecules have been characterized by single‐crystal X‐ray diffraction, 183W and 29Si NMR spectroscopy, IR spectroscopy, thermogravimetric analysis (TGA), and SEM/energy‐dispersive X‐ray (EDX) microscopy. The three compounds obtained here exemplify the influence of pH on the condensation of tetravalent cations and open a new route toward the stabilization of polynuclear tetravalent clusters by nucleophilic O‐donating POM species.

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Section: Resultscontrasting

confidence: 62%

Influence of the pH on the Condensation of Tetravalent Cerium Cations in Association with [α‐SiW₉O₃₄]^10– Leading to the Formation of a Ce₆O₄(OH)₄ Core

et al. 2016

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“…Such clusters may play an important role in crystallization of fluorite‐like CeO 2 and defective fluorite‐like (bixbyite‐like) Ce 2 O 3 . There are several experimental reports on the synthesis of chemical compounds containing Ce 6 O 8 fragments …”

Section: Resultsmentioning

confidence: 99%

“…In this article, we predict a structure and explore electronic and thermodynamic properties of a lanthanide oxide cluster Ce 6 O 8 featuring the first example of d‐AO‐based spherical σ aromaticity. As a matter of fact, the synthesis of the NH 4 [Ce 6 (μ 3 O) 5 (μ 3 OH) 3 (μ 2 ‐C 6 H 5 COO) 9 (NO 3 ) 3 (DMF) 3 ]*DMF*H 2 O compound containing Ce 6 O 8 core has already been reported . In general, our findings suggest that d‐AO spherical aromaticity may exist in many multinuclear transition metal and lanthanide oxide compounds.…”

Section: Introductionmentioning

confidence: 99%

d‐AO spherical aromaticity in Ce₆O₈

Oganov

Popov

et al. 2015

J Comput Chem

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After the first introduction of π aromaticity in chemistry to explain the bonding, structure, and reactivity of benzene and its derivatives, this concept was further applied to many other compounds featuring other types of aromaticity (i.e., σ, δ). Thus far, there have been no reports on d-AO-based spherical σ aromaticity. Here, we predict a highly stable bare Ce6O8 cluster of a spherical shape using evolutionary algorithm USPEX and DFT + U calculations. Natural bond orbital analysis, adaptive natural density partitioning algorithm, electron localization function, and partial charge plots demonstrate that bare Ce6O8 cluster exhibits d-AO spherical σ aromaticity, thus explaining its exotic geometry and stability. Ce6O8 complex plays an important role in many reactions and is known to exist in many forms, such as in NH4[Ce6(μ(3)O)5(μ(3)OH)3(μ(2)-C6H5COO)9(NO3)3(DMF)3]*DMF*H2O compound, which is prepared under room temperature, and acts as an oxidizing agent.

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“…Furthermore, the rare earth series offers the advantage of having exquisitely tunable ionic radii that enables sequential modifications in the properties of compounds derived from these elements. Examples of such tetravalent f element clusters include hexanuclear Ce IV carboxylates that can be used as oxidants in organic synthesis [13] and mixed Ce IV /Ln III clusters where both metal-based and ligand-based luminescence occur; [14] 5f element clusters are far more rare. However, dodecanuclear thorium clusters with a nitride core have [ been described.…”

Section: Introductionmentioning

confidence: 99%

Self‐Assembly of Hexanuclear Clusters of 4f and 5f Elements with Cation Specificity

et al. 2011

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Six hexanuclear clusters of 4f and 5f elements were synthesized by room‐temperature slow concentration experiments. Cerium(IV), thorium(IV), and plutonium(IV) each form two different hexanuclear clusters, among which the cerium and plutonium clusters are isotypic, whereas the thorium clusters show more diversity. The change in ionic radii of approximately 0.08 Å between these different metal ions tunes the cavity size so that NH4+ (1.48 Å) has the right dimensions to assemble the cerium and plutonium clusters, whereas Cs+ (1.69 Å) is necessary to assemble the thorium clusters. If these cations are not used in the reactions, only amorphous material is obtained.

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A hexanuclear cerium(IV) cluster with mixed coordination environment

Cited by 55 publications

References 15 publications

Influence of the pH on the Condensation of Tetravalent Cerium Cations in Association with [α‐SiW₉O₃₄]^10– Leading to the Formation of a Ce₆O₄(OH)₄ Core

Influence of the pH on the Condensation of Tetravalent Cerium Cations in Association with [α‐SiW₉O₃₄]^10– Leading to the Formation of a Ce₆O₄(OH)₄ Core

d‐AO spherical aromaticity in Ce₆O₈

Self‐Assembly of Hexanuclear Clusters of 4f and 5f Elements with Cation Specificity

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A hexanuclear cerium(IV) cluster with mixed coordination environment

Cited by 55 publications

References 15 publications

Influence of the pH on the Condensation of Tetravalent Cerium Cations in Association with [α‐SiW9O34]10– Leading to the Formation of a Ce6O4(OH)4 Core

Influence of the pH on the Condensation of Tetravalent Cerium Cations in Association with [α‐SiW9O34]10– Leading to the Formation of a Ce6O4(OH)4 Core

d‐AO spherical aromaticity in Ce6O8

Self‐Assembly of Hexanuclear Clusters of 4f and 5f Elements with Cation Specificity

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Product

Resources

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Influence of the pH on the Condensation of Tetravalent Cerium Cations in Association with [α‐SiW₉O₃₄]^10– Leading to the Formation of a Ce₆O₄(OH)₄ Core

Influence of the pH on the Condensation of Tetravalent Cerium Cations in Association with [α‐SiW₉O₃₄]^10– Leading to the Formation of a Ce₆O₄(OH)₄ Core

d‐AO spherical aromaticity in Ce₆O₈