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Synthesis and structural chemistry of novel heteropolymolybdates and -tungstates

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Molecular Engineering

Abstract

The chemistry of polynuclear oxometalate anions is dominated by molybdenum and tungsten in their highest oxidation state. During the past twenty years this class of compounds has attracted much attention because of their variable applications, e.g. as reagents in analytical procedures, as industrial catalysts and as potential anticancer drugs.

In order to obtain model systems for the investigation of the catalytic activity of heteropolyanions we have synthesized and structurally characterized some organo derivatives of polyoxoanions. We secondly focus on Sb(III) and Bi(III) heteropolytungstates to examine the important influence of the unshared electron pair on the resulting structures and properties. Some of these compounds may be regarded as supramolecular aggregates showing inclusion phenomena.

In 9 two [SbW9O33]9− anions are linked by a set of six sodium ions forming a nearly planar hexagon. The sodium ions are enveloped by an oxygen cage formed by terminal oxygen atoms of the polyanions and by water molecules. Furthermore, the four anions [Sb2W22O74(OH)2]12−, [Sb2W20Fe2O70(H2O)6]8−, [Sb2W20Co2O70(H2O)6]10− and [Bi2W20Fe2O68(OH)2(H2O)6]6− (in10, 11, 12, 13) may be regarded as transition metal complexes of novel [Sb2W20O70]14− or [Bi2W20O70]14− anions which are serving as ligands. The octahedral coordination sphere of each transition metal is formed by three oxygen atoms of the anion and completed by three water molecules. The Sb(III) heteropolyanion, [Na2Sb8W36O132(H2O)4]22− in (14) includes two sodium and four antimony ions besides four water molecules. Each anion consists of four β-B-SbW9-Keggin fragments linked together by four SbO4-groups, incorporating two sodium and four water molecules effecting an additional connection of the subunits.

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  1. Institute of Inorganic Chemistry, University of Münster, Wilhelm-Klemm-Straße 8, D-48149, Münster, Germany

    B. Krebs & R. Klein

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  1. B. Krebs
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Krebs, B., Klein, R. Synthesis and structural chemistry of novel heteropolymolybdates and -tungstates. Mol Eng 3, 43–59 (1993). https://doi.org/10.1007/BF00999623

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