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Issue 13, 2003
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Manganous heteropolytungstates. Synthesis and heteroatom effects in Wells–Dawson-derived sandwich complexes

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Abstract

A tetranuclear manganous Wells–Dawson sandwich-type polyoxometalate has been synthesized by the reaction of α-Na12(As2W15O56) with an aqueous solution of MnCl2·4H2O. The structure of this complex, αββα-Na16(MnIIOH2)2MnII2(As2W15O56)2·55H2O (Na1), was determined by single-crystal X-ray crystallography (a = 14.5230(12) Å, b = 14.7104(13) Å, c = 19.8927(17) Å, α = 84.326(2)°, β = 81.709(2)°, γ = 65.584(2)°, triclinic, R1 = 6.2%, based on 26721 independent reflections) and is similar to the phosphorus analogue, αββα-Na16(MnIIOH2)2MnII2(P2W15O56)2 (Na2). Magnetization studies confirm that both Na1 and Na2 show antiferromagnetic coupling of the four Mn(II) centers. Despite the structural similarities, electrochemical studies reveal that the presence of arsenic shifts the Mn waves to more positive potentials. Catalytic studies confirm that 1 is a significantly better catalyst than 2 for the H2O2-based epoxidation of cis-cyclooctene, cyclohexene, and 1-hexene.

Graphical abstract: Manganous heteropolytungstates. Synthesis and heteroatom effects in Wells–Dawson-derived sandwich complexes

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Publication details

The article was received on 17 Apr 2003, accepted on 19 May 2003 and first published on 06 Jun 2003


Article type: Paper
DOI: 10.1039/B304255C
Citation: Dalton Trans., 2003,0, 2646-2650
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    Manganous heteropolytungstates. Synthesis and heteroatom effects in Wells–Dawson-derived sandwich complexes

    I. M. Mbomekalle, B. Keita, L. Nadjo, P. Berthet, W. A. Neiwert, C. L. Hill, M. D. Ritorto and T. M. Anderson, Dalton Trans., 2003, 0, 2646
    DOI: 10.1039/B304255C

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