The sulfates Nb2O2(SO4)3, MoO2(SO4), WO(SO4)2, and two modifications of Re2O5(SO4)2 have been synthesized by the solvothermal reaction of NbCl5, WOCl4, Re2O7(H2O)2, and MoO3 with sulfuric acid/SO3 mixtures at temperatures between 200 and 300 °C. Besides the X-ray crystal structure determination of all compounds, the thermal behavior was investigated using thermogravimetric studies. WO(SO4)2 (monoclinic, P21/n, a = 7.453(1) A, b = 11.8232(8) A, c = 7.881(1) A, β = 107.92(2)°, V = 660.7(1) A3, Z = 4) and both modifications of Re2O5(SO4)2 (I: orthorhombic, Pba2, a = 9.649(1) A, b = 8.4260(8) A, c = 5.9075(7) A, V = 480.27(9) A3, Z = 2; II: orthorhombic, Pbcm, a = 7.1544(3) A, b = 7.1619(3) A, c = 16.8551(7) A, V = 863.64(6) A3, Z = 4) are the first structurally characterized examples of tungsten and rhenium oxide sulfates. Their crystal structure contains layers of sulfate connected [W═O] moieties or [Re2O5] units, respectively. The cohesion between layers is realized through weak M−O contacts (343−380 pm). ...

Sulfates of the refractory metals: crystal structure and thermal behavior of Nb2O2(SO4)3, MoO2(SO4), WO(SO4)2, and two modifications of Re2O5(SO4)2.

It is shown that a number of phosphates ionize in sulfuric acid to give the P(OH)4+ ion. Triphenyl phosphine and triethyl phosphate are fully protonated but phosphorus oxyfluoride and phosphorus oxychloride are shown to be nonelectrolytes.Ammonium metavanadate and vanadium pentoxide give the acid H[VO(HSO4)4] and there is evidence that the dimer H[V2O3(HSO4)6] and possibly higher polymers are present in increasing amounts with increasing concentration.

The sulfuric acid solvent system: part viii. solutions of some phosphorus(v) and vanadium(v) compounds

Deep-blue single crystals of MoO(HSO4)(SO4) are prepared from Mo(CO)6 in oleum (sealed glass ampule, 200 °C, 2 d)

Stabilizing Low‐Valent Refractory Metals in a Strongly Oxidizing Medium: The First Molybdenum(V) Sulfate—MoO(HSO4)(SO4)—from Mo(CO)6 in Oleum

Forschungsrichtungen in der Chemie des Germaniums

4 – Inorganic Halides and Oxyhalides as Solvents

Es werden die gunstigsten Bedingungen fur das Bestehen von isolierten Ionen hoher Wertigkeit in festen Korpern diskutiert. Auf Grund dieser Uberlegungen wurden Metallhalogenide und-oxyhalogenide mit SO3 in Losung von SO2Cl2 zu Sulfaten umgesetzt. So wurden erhalten Ti(SO4)2, Sn(SO4)2, U(SO4)2, V2O(SO4)4, Sb2O(SO4)4, CrO(SO4)2, MoO(SO4)2, WO(SO4)2. Die Substanzen sind hochst wasserempfindlich, zersetzen sich bei 100 bis 200° und sind farblos oder schwach gefarbt.

E. Hayek

Papers

Sulfate von Metallen hoher Wertigkeitsstufe