Structural investigation of tetraperoxo complexes of Mo(VI) and W(VI)

• Published in: Journal of solid state chemistry 2009-04, Vol.182 (4), p.973-982
• Main Authors: Grzywa, M., Łasocha, W., Rutkowska-Żbik, D.
• Format: Article
• Language: English
• Subjects: ALKALI METAL COMPOUNDS; AQUEOUS SOLUTIONS; CALCULATION METHODS; CESIUM COMPOUNDS; CHEMICAL ANALYSIS; COHERENT SCATTERING; COMPLEXES; CRYSTAL STRUCTURE; CRYSTALLOGRAPHY; CRYSTALS; DENSITY FUNCTIONAL METHOD; DFT; DIFFRACTION; DISPERSIONS; HOMOGENEOUS MIXTURES; HYDROGEN COMPOUNDS; HYDROGEN PEROXIDE; INFRARED SPECTRA; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; MIXTURES; MOLYBDENUM COMPLEXES; MONOCRYSTALS; OXYGEN COMPOUNDS; PEROXIDES; Peroxometalates; Peroxomolybdates; Peroxotungstates; Peroxovanadates; QUANTITATIVE CHEMICAL ANALYSIS; RUBIDIUM COMPOUNDS; SCATTERING; SODIUM COMPOUNDS; SOLUTIONS; SPECTRA; STABILITY; TITRATION; TRANSITION ELEMENT COMPLEXES; TUNGSTEN COMPLEXES; VARIATIONAL METHODS; VOLUMETRIC ANALYSIS; X-RAY DIFFRACTION
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/j.jssc.2009.01.009

The family of very unstable tetraperoxo compounds has been prepared from aqueous solutions containing H 2O 2 and salts of Mo(VI) or W(VI). The crystal structures of Na 2[Mo(O 2) 4]·4H 2O and Na 2[W(O 2) 4]·4H 2O have been determined from single-crystal data, while the crystal structures of Rb 2[Mo(O 2) 4], Cs 2[Mo(O 2) 4], Rb 2[W(O 2) 4] and Cs 2[W(O 2) 4] have been determined from powder X-ray diffraction data. The compounds were also characterised by IR spectroscopy and the number of peroxo groups was determined by titration methods. By means of the density functional theory (DFT) method, the geometry and stability of tetraperoxo complexes have been studied. Even though in all tetraperoxo complexes the central atom Mo(VI), W(VI) or V(V) is surrounded by four peroxo groups and the geometry of the [ Me(O 2) 4] n− anion is essentially the same, the investigated compounds differ in stability and colour and crystallise in different crystallographic systems. The family of tetraperoxo compounds of Mo(VI) or W(VI) have been obtained. Its crystal structures from single-crystal and from powder X-ray diffraction data have been determined. The compounds were characterised by IR spectroscopy and analytical methods. By means of the density functional theory (DFT) method, the geometry and stability of tetraperoxo complexes have been studied.