Issue 19, 2015

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

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.

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

Supplementary files

Article information

Article type
Paper
Submitted
26 Jan 2015
Accepted
30 Mar 2015
First published
30 Mar 2015

Dalton Trans., 2015,44, 8839-8845

Author version available

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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