Homo‐ and Heterovalent Polynuclear Cerium and Cerium/Manganese Aggregates

Mereacre, Valeriu; Ako, Ayuk M.; Akhtar, Muhammad Nadeem; Lindemann, Anja; Anson, Christopher E.; Powell, Annie K.

doi:10.1002/hlca.200900192

Cited by 73 publications

(37 citation statements)

References 105 publications

(18 reference statements)

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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%

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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“…Ammonium cerium(IV) nitrate is also a reagent for cleavage of proteins [11]. The cerium carboxylate metallo-organic frameworks have interesting properties [12][13][14][15]. In this study we have been able to isolate and characterise a mixed ligand containing cerium(IV) complex which is also an useful oxidant.…”

mentioning

confidence: 94%

A hexanuclear cerium(IV) cluster with mixed coordination environment

Das

Sarma

Baruah

2010

Inorganic Chemistry Communications

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Homo‐ and Heterovalent Polynuclear Cerium and Cerium/Manganese Aggregates

Cited by 73 publications

References 105 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

A hexanuclear cerium(IV) cluster with mixed coordination environment

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Homo‐ and Heterovalent Polynuclear Cerium and Cerium/Manganese Aggregates

Cited by 73 publications

References 105 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

A hexanuclear cerium(IV) cluster with mixed coordination environment

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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