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2005
Iron
I 7100
19- 023
Structure, Electrochemistry, and Magnetism of the Iron(III)-Substituted Keggin
Dimer, [Fe6(OH)3(A-α-GeW9O34(OH)3)2]11-. — Title compound (V) crystallizes in the
monoclinic space group C2/m with Z = 4 (single crystal XRD). The polyanion of (V)
consists of two (A-α-GeW9O34) Keggin moieties linked via six Fe3+ ions, leading to a
double-sandwich structure. Electrochemical studies reveal that (V) is stable in the pH
range from 3 to at least 7. In pH 3 media, the reduction of the six Fe3+ centers is featured
by a single voltammetric wave for the most supporting electrolytes used. The acetate
medium induces a partial splitting of the wave and this separation is enhanced with
increasing pH. Remarkable efficiency of (V) in the electrocatalytic reduction of nitrite,
nitric oxide, and nitrate is demonstrated. Magnetic susceptibility measurements indicate a diamagnetic (ST = 0) ground state which is confirmed by EPR. — (BI, L.-H.;
KORTZ*, U.; NELLUTLA, S.; STOWE, A. C.; VAN TOL, J.; DALAL, N. S.; KEITA,
B.; NADJO, L.; Inorg. Chem. 44 (2005) 4, 896-903; Sch. Eng. Sci., Intern. Univ.
Bremen, D-28759 Bremen, Germany; Eng.) — Schramke
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