Unveiling of a Trinuclear Cyclic Peroxidovanadate: A Potential Oxidant in Vanadium-Catalyzed Reactions

The first peroxidovanadium trimer was prepared in the form of its tetrabutylammonium salt, (NBu4)3[V3O3(O2)6]·2H2O. Its X-ray structure analysis revealed a unique cyclic structure of the [V3O3(O2)6]3– ion incorporating the yet unobserved μ3-η2:η1:η1 coordination mode of one of its peroxido ligands....

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Bibliographic Details
Published in:Inorganic chemistry 2015-07, Vol.54 (13), p.6306-6311
Main Authors: Krivosudský, Lukáš, Schwendt, Peter, Gyepes, Róbert
Format: Article
Language:English
Subjects:
Aqueous solutions
Formations
Ligands
Oligomers
Solvents
Structural analysis
Trimers
X-rays
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Summary:The first peroxidovanadium trimer was prepared in the form of its tetrabutylammonium salt, (NBu4)3[V3O3(O2)6]·2H2O. Its X-ray structure analysis revealed a unique cyclic structure of the [V3O3(O2)6]3– ion incorporating the yet unobserved μ3-η2:η1:η1 coordination mode of one of its peroxido ligands. While relatively stable in nonaqueous solvents, the [V3O3(O2)6]3– ion quickly decomposes in diluted aqueous solutions. A higher vanadium concentration or a higher CH3CN content in the mixed CH3CN/H2O solvent facilitates the formation of oligomers [V2O2(O2)4(H2O)]2– and [V3O3(O2)6]3–. 51V NMR investigations indicated that the trinuclear species is incorporated in vanadium-catalyzed oxidations in the presence of H2O2.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.5b00600