Reactions of [Ru(NO)Cl5]2− with pseudotrilacunary {XW9O33}9− (X = AsIII, SbIII) anions. Issue 42 (9th October 2019)

• Record Type: Journal Article
• Authors: Mukhacheva, Anna A.; Shmakova, Alexandra A.; Volchek, Victoria V.; Romanova, Tamara E.; Benassi, Enrico; Gushchin, Artem L.; Yanshole, Vadim; Sheven, Dmitri G.; Kompankov, Nikolay B.; Abramov, Pavel A.; Sokolov, Maxim N.
• Is Part Of: Dalton transactions. Volume 48:Issue 42(2019)
• Page Start: 15989
• Page End: 15999
• Publication Date: 2019-10-09
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c9dt03328a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Reactions of [Ru(NO)Cl5 ] 2− with pseudotrivacant B-α-[XW9 O33 ] 9− (X = As III, Sb III ) result in novel nitrosoruthenium-substituted polyanions. Abstract : Reactions of [Ru(NO)Cl5 ] 2− with pseudotrivacant B-α-[XW9 O33 ] 9− (X = As III, Sb III ) at 160 °C result in the rearrangement of polyoxometalate backbones into {XM18 } structures. In the case of arsenic, oxidation of As III to As V takes place with the formation of a mixture of plenary and monosubstituted Dawson [As2 W18 O62 ] 6− and [As2 W17 Ru(NO)O61 ] 7− anions, of which the latter was isolated as Me2 NH2 + (DMA-1a and DMA-1b ) and Bu4 N + (Bu4 N-1 ) salts and fully characterized. Both α1 and α2 isomers of [As2 W17 Ru(NO)O61 ] 7− were present in the reaction mixture; pure [α2 -As2 W17 Ru(NO)O61 ] 7− was isolated as the Bu4 N + salt. In the case of antimony, [SbW9 O33 ] 9− is converted into a mixture of [SbW18 O60 ] 9− and [SbW17 {Ru(NO)}O59 ] 10− . The formation of trisubstituted [SbW15 {Ru(NO)}3 O57 ] 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.