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Reactions of [Ru(NO)Cl5]2− with pseudotrilacunary {XW9O33}9− (X = AsIII, SbIII) anions

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Abstract

Reactions of [Ru(NO)Cl5]2− with pseudotrivacant B-α-[XW9O33]9− (X = AsIII, SbIII) at 160 °C result in the rearrangement of polyoxometalate backbones into {XM18} structures. In the case of arsenic, oxidation of AsIII to AsV takes place with the formation of a mixture of plenary and monosubstituted Dawson [As2W18O62]6− and [As2W17Ru(NO)O61]7− anions, of which the latter was isolated as Me2NH2+ (DMA-1a and DMA-1b) and Bu4N+ (Bu4N-1) salts and fully characterized. Both α1 and α2 isomers of [As2W17Ru(NO)O61]7− were present in the reaction mixture; pure [α2-As2W17Ru(NO)O61]7− was isolated as the Bu4N+ salt. In the case of antimony, [SbW9O33]9− is converted into a mixture of [SbW18O60]9− and [SbW17{Ru(NO)}O59]10−. The formation of trisubstituted [SbW15{Ru(NO)}3O57]12− as a minor byproduct was detected by HPLC-ICP-AES. The monosubstituted [SbW17{Ru(NO)}O59]10− anion was isolated as DMAH+ (DMA-2) and mixed inorganic cation (CsKNa-2) salts and characterized by XRD, HPLC-ICP-AES, EA and TGA techniques. X-ray analysis shows the presence of the {Ru(NO)}-group in the 6-membered (“equatorial”) belt of the Sb-free hemisphere. The experimental findings were confirmed and interpreted by means of quantum chemical calculations.

Graphical abstract: Reactions of [Ru(NO)Cl5]2− with pseudotrilacunary {XW9O33}9− (X = AsIII, SbIII) anions

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Publication details

The article was received on 15 Aug 2019, accepted on 26 Sep 2019 and first published on 26 Sep 2019


Article type: Paper
DOI: 10.1039/C9DT03328A
Dalton Trans., 2019, Advance Article

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    Reactions of [Ru(NO)Cl5]2− with pseudotrilacunary {XW9O33}9− (X = AsIII, SbIII) anions

    A. A. Mukhacheva, A. A. Shmakova, V. V. Volchek, T. E. Romanova, E. Benassi, A. L. Gushchin, V. Yanshole, D. G. Sheven, N. B. Kompankov, P. A. Abramov and M. N. Sokolov, Dalton Trans., 2019, Advance Article , DOI: 10.1039/C9DT03328A

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