Selenate as a novel ligand for keplerate chemistry. New {W72Mo60} keplerates with selenates inside the cavity

Vladimir S. Korenev; Pavel A. Abramov; Cristian Vicent; Artem A. Zhdanov; Alphiya R. Tsygankova; Maxim N. Sokolov; Vladimir P. Fedin

doi:10.1039/C5DT00349K

Selenate as a novel ligand for keplerate chemistry. New {W₇₂Mo₆₀} keplerates with selenates inside the cavity†‡

Vladimir S. Korenev,*^ab Pavel A. Abramov,^ab Cristian Vicent,^c Artem A. Zhdanov,^ab Alphiya R. Tsygankova,^a Maxim N. Sokolov^ab and Vladimir P. Fedin^ab

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^a Nikolaev Institute of Inorganic Chemistry SB RAS, Prospect Lavrentyeva 3, 630090 Novosibirsk, Russia
E-mail: wkorenev@niic.nsc.ru
Fax: +7 383 330 9089
Tel: +7 383 316 5845

^b Novosibirsk State University, Pirogova Street 2, 630090 Novosibirsk, Russia

^c Serveis Centrals d'Instrumentacio Cientifica, Universitat Jaume I, Avda. Sos Baynat s/n, Castello, Spain

Abstract

The synthesis and characterization of three novel keplerate-type compounds containing the {W₇₂Mo₆₀} mixed-metal core are reported. Complexes (NH₄)₇₂[{W₆O₂₁(H₂O)₆}₁₂{Mo₂O₄(SeO₄)}₃₀]·150H₂O·6(NH₄)₂SeO₄ (1a) and (NH₄)₂₅(NH₂Me₂)₄₇[{W₆O₂₁(H₂O)₆}₁₂{Mo₂O₄(SeO₄)}₃₀]·130H₂O·3(NH₄)₂SeO₄ (1b) were prepared by ligand substitution from the acetate anionic complex [{W₆O₂₁(H₂O)₅(CH₃COO)_0.5}₁₂{Mo₂O₄(CH₃COO)}₃₀]⁴⁸⁻ and selenate. The selenate anions in keplerate ions [{W₆O₂₁(H₂O)₆}₁₂{Mo₂O₄(SeO₄)}₃₀]⁷²⁻ are very labile and easily aquate with the formation of [{W₆O₂₁(H₂O)₆}₁₂{Mo₂O₄}₃₀(SeO₄)₂₀(H₂O)₂₀]⁵²⁻, which was isolated as (NH₄)₂₀(NH₂Me₂)₃₂[{W₆O₂₁(H₂O)₆}₁₂{Mo₂O₄}₃₀(SeO₄)₂₀(H₂O)₂₀]·150H₂O (2) and structurally characterized. In the crystal structure of 2 selenate has several coordination modes, preferentially bonding to the {Mo₂O₄}²⁺ units, and, additionally, to the {(W)W₅} pentagonal blocks. The compounds have been characterized by elemental analysis, Raman, IR and ⁷⁷Se NMR spectroscopy, and by ESI mass spectrometry. Capillary electrophoresis was used for characterization of keplerates in solution for the first time.

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DOI: https://doi.org/10.1039/C5DT00349K
Article type: Paper
Submitted: 26 Jan 2015
Accepted: 30 Mar 2015
First published: 30 Mar 2015

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Dalton Trans., 2015,44, 8839-8845

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Selenate as a novel ligand for keplerate chemistry. New {W₇₂Mo₆₀} keplerates with selenates inside the cavity

V. S. Korenev, P. A. Abramov, C. Vicent, A. A. Zhdanov, A. R. Tsygankova, M. N. Sokolov and V. P. Fedin, Dalton Trans., 2015, 44, 8839 DOI: 10.1039/C5DT00349K

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