Syntheses and characterization of {gamma}-[SiW{sub 10}M{sub 2}S{sub 2}O{sub 38}]{sup 6{minus}} (M = Mo{sup V}, W{sup V}). Two Keggin oxothio heteropolyanions with a metal-metal bond
- Universite de Versailles Saint Quentin, Versailles (France); and others
The oxothio polyanions {gamma}-[SiW {sub 10}M{sub 2}S{sub 2}O{sub 38}]{sup 6{minus}} (M = Mo{sup V}, W{sup V}) were obtained through stereospecific addition of the dication [M{sub 2}S{sub 2}O{sub 2}]{sup 2+} (M = Mo, W) to the divacant {gamma}-[SiW {sub 10}O{sub 36}]{sup 8{minus}} anion in dimethylformamide. These compounds were isolated as crystals and are stable in usual organic solvents and in aqueous medium from pH = 1 to pH = 7. NEt{sub 4}Cs{sub 3}H{sub 2}[SiW {sub 10}Mo{sub 2}S{sub 2}O{sub 38}]{lg_bullet}6H{sub 2}O (a {gamma}-isomer derived from the {alpha} Keggin structure capped by the [Mo{sub 2}S{sub 2}O{sub 2}]{sup 2+} fragment containing a metal-metal bond) crystallizes in the triclinic space group P1 with a = 12.050(3) {Angstrom}, b = 12.695(2) {Angstrom}, c = 20.111(4) {Angstrom}, {alpha} = 74.35(2){degrees}, {Beta} = 86.83(2){degrees}, {gamma} - 63.50(2){degrees}, Z = 2. NEt{sub 4{minus}}Cs{sub 5}[SiW {sub 12}S{sub 2}O{sub 28}]{lg_bullet}7H{sub 2}O is isostructural and crystallizes in the triclinic space group P1 with a = 12.197(4) {Angstrom}, b = 12.714(3) {Angstrom}, c = 20.298(3) {Angstrom}, {alpha} = 74.75(1) {Angstrom}, {Beta} = 86.48(2){degrees}, {gamma} = 61.80(2){degrees}, Z = 2. {sup 183}W NMR spectra of Li{sup +} salts in aqueous solution agree with the solid state structures and reveal 100% purity for both anions. Polarographic, infrared and UV-vis data are also given.
- OSTI ID:
- 391340
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 11 Vol. 35; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
Similar Records
Polyoxoanions derived from A-. beta. -SiW sub 9 O sub 34 sup 10 minus : Synthesis and crystallographic and sup 183 W NMR characterization of Si sub 2 W sub 18 Zr sub 3 O sub 71 H sub 3 sup 11 minus , including its organic solvent soluble Bu sub 4 N sup + salt
EPR studies of S(M(CO) sub 5 ) sub 2 sup minus radicals (M = Cr, W) trapped in single crystals of PPN sup + HS(M(CO) sub 5 ) sub 2 sup minus