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Issue 13, 2013
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Amine templated open-framework vanadium(III) phosphites with catalytic properties

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Abstract

Four novel amine templated open-framework vanadium(III) phosphites with the formula (C5N2H14)0.5[V(H2O)(HPO3)2], 1 (C5N2H14 = 2-methylpiperazinium), and (L)4−x(H3O)x[V9(H2O)6(HPO3)14−y(HPO4)y(H2PO3)3−z(H2PO4)znH2O (2, L = cyclopentylammonium, x = 0, y = 3.5, z = 3, n = 0; 3, L = cyclohexylammonium, x = 1, y = 0, z = 0.6, n = 2.33; 4, L = cycloheptylammonium, x = 1, y = 0, z = 0, n = 2.33) were synthesized employing solvothermal reactions and characterized by single-crystal X-ray diffraction, ICP-AES and elemental analyses, thermogravimetric and thermodiffractometric analyses, and IR and UV/vis spectroscopy. Single-crystal data indicate that 1 crystallizes in the triclinic system, space group P[1 with combining macron], whereas 2, 3 and 4 crystallize in the hexagonal space group P63/m. Compound 1 has a two-dimensional motif with anionic sheets of [V(H2O)(HPO3)2] formula, whose charge is compensated by the 2-methylpiperazinium cations embedded between the layers. In contrast, 2, 3 and 4 present a pillar-layer network giving rise to a three-dimensional framework containing intersecting 16-ring channels with the primary amine templates and the crystallization water molecules enclosed in them. 1, 2, 3 and 4 behave as heterogeneous catalysts for the selective oxidation of alkyl aryl sulfides, with tert-butylhydroperoxide (TBHP) as the oxidizing agent, being active, selective and recyclable for several successive cycles of reaction.

Graphical abstract: Amine templated open-framework vanadium(iii) phosphites with catalytic properties

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Publication details

The article was received on 28 Sep 2012, accepted on 02 Jan 2013 and first published on 03 Jan 2013


Article type: Paper
DOI: 10.1039/C2DT32286B
Citation: Dalton Trans., 2013,42, 4500-4512
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    Amine templated open-framework vanadium(III) phosphites with catalytic properties

    J. Orive, E. S. Larrea, R. Fernández de Luis, M. Iglesias, J. L. Mesa, T. Rojo and M. I. Arriortua, Dalton Trans., 2013, 42, 4500
    DOI: 10.1039/C2DT32286B

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