A Layered Manganese(IV)-Containing Heteropolyvanadate with a 1:14 Stoichiometry
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A novel manganese(IV)-containing symmetrical heteropolyvanadate was prepared by the transformation of K7[MnV13O38]·18H2O (K7MnV13) to K4Li2[MnV14O40]·21H2O (1) at pH 4. The heteropolyanion [MnV14O40]6– (MnV14) is composed of a MnO6 octahedron surrounded by 14 edge-sharing VO6 octahedra. The simplified representation of MnV14 has a new topology termed jba1 with a total point symbol of {310}2{314.47}4{318.410}8{344.446.5}. In the crystal lattice of 1, MnV14 packs with potassium ions, forming a 2D layered K2[MnV14O40]4– network (ABABAB...). Four K+ ions cap the four square O4 faces of MnV14, apparently stabilizing the heteropolyanion. Compound 1 catalyzes the t-BuOOH-based oxidation of 2-chloroethyl ethyl sulfide (a mustard gas simulant). The magnetic and catalytic properties of 1 are discussed.
