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Dinuclear Mo(VI) complexes with 4-aminobenzoylhydrazone derivatives: a solid-state and solution study

An important part of supramolecular chemistry refers to the coordination-driven self- assembly. Recently, the design and synthesis of supramolecular coordination complexes have attracted significant attention in various fields due to the interesting molecular architectures and/or a wide variety of properties, e.g. redox, magnetic, catalytic or optical. Although polydentate ligands have played a substantial role in coordination chemistry of molybdenum(VI), their use as structural elements in metallosupramolecular chemistry has received considerably less attention. Therefore, three polydentate aroylhydrazone ligands (H2L1–3) were selected to investigate if they could serve as organic linkers for the cis-octahedral complex containing the {; ; ; ; ; ; MoO2}; ; ; ; ; ; 2+ core. [1] Hydrazones were prepared by the reaction of 4- aminobenzhydrazide with salicylaldehyde (H2L1), 3- methoxysalicylaldehyde (H2L2) or 4- methoxysalicylaldehyde (H2L3). Dinuclear dioxidomolybdenum(VI) complexes of selected hydrazones, [MoO2(L1–3)]2, were synthesized by the reaction of [MoO2(acac)2] and the corresponding ligand. All isolated complexes were characterized in the solid state by means of elemental and thermogravimetric analysis, infrared spectroscopy and X-ray diffraction methods (PXRD and SCXRD when suitable). Furthermore, the complexes were explored by one- and two-dimensional NMR spectroscopic techniques in dmso-d6. In all complexes, the doubly deprotonated form of aroylhydrazone is coordinated to {; ; ; ; ; ; MoO2}; ; ; ; ; ; 2+ core through the O, N, O donor atoms. The sixth coordination site of molybdenum is occupied by the amino nitrogen of the neighboring hydrazone.

hydrazones ; molybdenum(VI) complexes ; X-ray diffraction ; NMR study

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