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

Anna A. Mukhacheva, Alexandra A. Shmakova, Victoria V. Volchek, Tamara E. Romanova, Enrico Benassi, Artem L. Gushchin, Vadim Yanshole, Dmitri G. Sheven, Nikolay B. Kompankov, Pavel A. Abramov, Maxim N. Sokolov

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)

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.

Original languageEnglish
Pages (from-to)15989-15999
Number of pages11
JournalDalton Transactions
Volume48
Issue number42
DOIs
Publication statusPublished - 14 Nov 2019

Keywords

  • WATER OXIDATION
  • STRUCTURAL-CHARACTERIZATION
  • ORGANOMETALLIC DERIVATIVES
  • ELECTROCHEMICAL-BEHAVIOR
  • PHOTOREDOX CHEMISTRY
  • GAMMA-CYCLODEXTRIN
  • CATALYTIC-ACTIVITY
  • AQUEOUS-SOLUTION
  • KEGGIN STRUCTURE
  • NOBLE-METALS

Fingerprint Dive into the research topics of 'Reactions of [Ru(NO)Cl<sub>5</sub>]<sup>2-</sup> with pseudotrilacunary {XW<sub>9</sub>O<sub>33</sub>}<sup>9-</sup> (X = As<sup>III</sup>, Sb<sup>III</sup>) anions'. Together they form a unique fingerprint.

Cite this