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242
Configurational Isomerism in Polyoxovanadates

graphical abstract

graphical abstract
Image Credit: © 2018, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

L.K. Mahnke, A. Kondinski, U. Warzok, C. Näther, J. van Leusen, C.A. Schalley, K.Y. Monakhov, P. Kögerler, W. Bensch – 2018

A water-soluble derivative of the polyoxovanadate {V15E6O42} (E = semimetal) archetype enables the study of cluster shell rearrangements driven by supramolecular interactions. A reaction unique to E = Sb, induced exclusively by ligand metathesis in peripheral [NiII(ethylenediamine)] counterions, results in the nearly quantitative formation of the metastable alpha1* conformational isomer of the {V14E8O42} cluster type. Contrary to all other polyoxovanadate shell architectures, this isomer comprises an inward-oriented vanadyl group and is ca. 50 and 12 kJ mol–1 higher in energy than the previously isolated alpha and beta isomers, respectively. We discuss this unexpected reaction in light of supramolecular Sb-O···V and Sb- O···Sb contacts manifested in {V14E8O42}2 dimers observed in the solid state. ESI MS experiments confirm the stability of these dimers also in solution and in the gas phase. DFT calculations indicate that other, as of yet elusive isomers might be accessible as well.

Title
242
Configurational Isomerism in Polyoxovanadates
Author
L.K. Mahnke, A. Kondinski, U. Warzok, C. Näther, J. van Leusen, C.A. Schalley, K.Y. Monakhov, P. Kögerler, W. Bensch
Date
2018-02-12
Identifier
DOI: 10.1002/anie.201712417 (English), 10.1002/ange.201712417 (German)
Citation
Angew. Chem. Int. Ed. 2018, 57, 2972-2975; Angew. Chem. 2018, 130, 3024-3028
Type
Text