ISSN:
1434-1948
Keywords:
Aminoalcohol ligands
;
Hydrogen bonds
;
Magnetic properties
;
Oxo complexes
;
Vanadium
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The aminoalcohol ligands diethanolamine (H2dea) and triethanolamine (H3tea) react with [VO(acac)2] to yield the tetranuclear oxovanadium(IV) complexes [{VO(dea)}2{VO(acac)}2(μ2-OMe)2] (1) and [{VO(Htea)}2{VO(acac)}2(μ2-OMe)2] (2). In the case of the potentially bridging aminoalcohol ligands N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine (H4edte) and N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine (H4edtp) the corresponding oxovanadium(IV) complexes could not be isolated. Instead after air oxidation the ligand supported binuclear oxovanadium(V) complexes [{VO(acac)}2(edte)] (3) and [{VO(acac)}2(edtp)] (4) are obtained. The reaction of the ligand H4edtp with ammonium meta-vanadate in methanol solution leads to the methoxy bridged binuclear oxovanadium(V) complex [(VO)2(edtp)(μ2-OMe)2] (5). The tetranuclear oxovanadium(IV) complexes can be isolated as crystalline compounds 1 · 2 MeOH and 2 · 2 MeOH and have been characterized by IR, UV/Vis, and ESR spectroscopy as well as cyclic voltammetry and magnetic susceptibility measurements. Single-crystal diffraction studies reveal that the complexes 1 and 2 contain a tetranuclear {(VO)4(μ3-OR)2(μ2-OR)4}2+ core composed of three different types of edge-shared binuclear units, whereas the oxovanadium(V) complexes 3, 4, and 5 posses binuclear structures, that are either ligand supported as in the case of 3 and 4 or contain a μ2-methoxy bridged{(VO)2(μ2-OR)2}4+ core as in the case of 5. ESR and magnetic data indicate a singlet ground state for 1 · 2 MeOH and 2 · 2 MeOH, although competing ferromagnetic exchange interactions are operative within the tetranuclear core structure. In the solid state compounds 1 · 2 MeOH and 2 · 2 MeOH hydrogen bridged supramolecular structures are found. The hydrogen bonding scheme of both compounds leads to the formation of a similar chain arrangement of the tetranuclear complexes 1 and 2.
Type of Medium:
Electronic Resource
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