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

doi:10.1039/c9dt03328a

Reactions of [Ru(NO)Cl₅]^2- with pseudotrilacunary {XW₉O₃₃}^9- (X = As^III, Sb^III) anions

Dalton Trans. 2019 Nov 14;48(42):15989-15999. doi: 10.1039/c9dt03328a. Epub 2019 Oct 9.

Affiliations

¹ Nikolaev Institute of Inorganic Chemistry, 3 Akad. Lavrentiev Ave, 630090, Novosibirsk, Russia. abramov@niic.nsc.ru and Novosibirsk State University, Pirogova str. 2, 630090, Novosibirsk, Russia. enrico.benassi@sns.it.
² Nikolaev Institute of Inorganic Chemistry, 3 Akad. Lavrentiev Ave, 630090, Novosibirsk, Russia. abramov@niic.nsc.ru.
³ Novosibirsk State University, Pirogova str. 2, 630090, Novosibirsk, Russia. enrico.benassi@sns.it and Lanzhou Institute of Chemical Physics, CAS, 10 Tianshui Middle Rd, Chengguan Qu, Lanzhou Shi, Gansu Sheng 730000, People's Republic of China.
⁴ Novosibirsk State University, Pirogova str. 2, 630090, Novosibirsk, Russia. enrico.benassi@sns.it and International Tomography Center, Institutskaya str. 3a, 630090, Novosibirsk, Russia.
⁵ Nikolaev Institute of Inorganic Chemistry, 3 Akad. Lavrentiev Ave, 630090, Novosibirsk, Russia. abramov@niic.nsc.ru and South Ural State University, Chelyabinsk, 454080, Russia.

PMID: 31595900
DOI: 10.1039/c9dt03328a

Abstract

Reactions of [Ru(NO)Cl₅]^2- with pseudotrivacant B-α-[XW₉O₃₃]^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 [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.