Change search
ReferencesLink to record
Permanent link

Direct link
Chemical equilibria in the uranyl(VI)-peroxide-carbonate system: identification of precursors for the formation of poly-peroxometallates
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.ORCID iD: 0000-0002-7552-1076
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
2012 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 41, no 38, 11635-11641 p.Article in journal (Refereed) Published
Abstract [en]

The focus of this study is on the identification of precursors in solution that might act as building blocks when solid uranyl(VI) poly-peroxometallate clusters containing peroxide and hydroxide bridges are formed. The precursors could be identified by using carbonate as an auxiliary ligand that prevented the formation of large clusters, such as the ones found in solids of fullerene type. Using data from potentiometric and NMR (O-17 and C-13) experiments we identified the following complexes and determined their equilibrium constants: (UO2)(2)(O-2)(CO3)(4)(6-), UO2(O-2)CO32-, UO2(O-2)(CO3)(2)(4-), (UO2)(2)(O-2)(CO3)(2)(2-), (UO2)(2)(O-2)(2)(CO3)(2-) and [UO2(O-2)(CO3)(5)(10-). The NMR spectra of the pentamer show that all uranyl and carbonate sites are equivalent, which is only consistent with a ring structure built from uranyl units linked by peroxide bridges with the carbonate coordinated "outside" the ring; this proposed structure is very similar to [UO2(O-2)(oxalate)](5)(10-) identified by Burns et al. (J. Am. Chem. Soc., 2009, 131, 16648; Inorg. Chem., 2012, 51, 2403) in K-10[UO2(O-2)(oxalate)](5)center dot(H2O)(13); similar ring structures where oxalate or carbonate has been replaced by hydroxide are important structure elements in solid poly-peroxometallate complexes. The equivalent uranyl sites in (UO2)(2)(O-2)(2)(CO3)(2-) suggest that the uranyl-units are linked by the carbonate ion and not by peroxide.

Place, publisher, year, edition, pages
2012. Vol. 41, no 38, 11635-11641 p.
Keyword [en]
Uranyl-Peroxide Nanoclusters, Clusters
National Category
Chemical Sciences
URN: urn:nbn:se:kth:diva-103780DOI: 10.1039/c2dt31282dISI: 000308655800016ScopusID: 2-s2.0-84870861313OAI: diva2:561651

QC 20121019

Available from: 2012-10-19 Created: 2012-10-19 Last updated: 2012-10-25Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full textScopus

Search in DiVA

By author/editor
Szabo, ZoltanGrenthe, Ingmar
By organisation
Organic Chemistry
In the same journal
Dalton Transactions
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 51 hits
ReferencesLink to record
Permanent link

Direct link