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
- Univ. of Oregon, Eugene (USA)
The reaction of A-{beta}-SiO{sub 9}O{sub 34}{sup 10{minus}} and ZrO{sup 2+} ions in aqueous solution, under conditions initially designed to give SiW{sub 9}Zr{sub 3}O{sub 40}{sup 10{minus}}, instead yields the new heteropolytungstate anion Si{sub 2}W{sub 18}Zr{sub 3}O{sub 71}H{sub 3}{sup 11{minus}}, isolated as its Bu{sub 4}N{sup +}, Me{sub 4}N{sup ++}, and Me{sub 3}NH{sup +} acid salts. These have been characterized by means of elemental analysis, TGA, IR spectroscopy, {sup 29}Si and {sup 183}W NMR spectroscopy, and, for the Bu{sub 4}N{sup +} salt, FAB mass spectroscopy. Structural questions left unanswered by the solution NMR studies were answered by a single-crystal x-ray structural analysis of the Me{sub 3}NH{sup +} salt, (Me{sub 3}NM){sub 10}H(Si{sub 2}W{sub 18}Zr{sub 3}O{sub 71}H{sub 3}){center dot}10H{sub 2}O (monoclinic, P2{sub 1}/n, a = 13.452 (3) {angstrom}, b = 43.416 (7) {angstrom}, c = 18.331 (4) {angstrom}, {beta} = 102.17 (2){degree}, Z = 4, Mo radiation, R = 0.055 for 8755 independent data with 1 {ge} 3{sigma}(I)). The crystallographic analysis shows the anion to have the composition (Zr{sub 3}(OH){sub 3}(A-{beta}-SiW{sub 9}O{sub 34}){sub 2}){sup 11{minus}}, with approximate D{sub 3h} symmetry. The equatorially placed Zr atoms are linked by OH atoms. Each Zr is also bonded to two oxygens of an edge-sharing pair of WO{sub 6} octahedra in each SiW{sub 9}O{sub 34} unit and each trigonal-prismatic ZrO{sub 6} group (average Zr-O = 2.11 (4) {angstrom}) is enlarged by two long Zr-O-(Si,W) bonds (average Zr-O = 2.83 (7) {angstrom}) normal to the prism faces. Possible reasons for the formation of Si{sub 2}W{sub 18}Zr{sub 3}, rather than SiW{sub 9}Zr{sub 3}, are discussed. 31 refs., 3 figs., 4 tabs.
- OSTI ID:
- 5112171
- Journal Information:
- Inorganic Chemistry; (USA), Vol. 28:8; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
SILICON COMPOUNDS
CRYSTAL STRUCTURE
ZIRCONIUM COMPOUNDS
EXPERIMENTAL DATA
NMR SPECTRA
SILICON 29
SYNTHESIS
TUNGSTEN 183
DATA
EVEN-ODD NUCLEI
HEAVY NUCLEI
INFORMATION
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
RADIOISOTOPES
SECONDS LIVING RADIOISOTOPES
SILICON ISOTOPES
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPOUNDS
TUNGSTEN ISOTOPES
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation