Peroxo-Zr/Hf-Containing Undecatungstosilicates and -Germanates
Autor(en): | Mal, Sib Sankar Nsouli, Nadeen H. Carraro, Mauro Sartorel, Andrea Scorrano, Gianfranco Oelrich, Holger Walder, Lorenz Bonchio, Marcella Kortz, Ulrich |
Stichwörter: | Chemistry; Chemistry, Inorganic & Nuclear; COMPLEXES; CRYSTAL-STRUCTURES; ORGANIC-LIGANDS; PROTON-TRANSFER; SUBSTITUTED POLYOXOTUNGSTATES; TH-IV; THORIUM(IV); U-VI IONS; ZIRCONIUM(IV); ZR-IV | Erscheinungsdatum: | 2010 | Herausgeber: | AMER CHEMICAL SOC | Journal: | INORGANIC CHEMISTRY | Volumen: | 49 | Ausgabe: | 1 | Startseite: | 7 | Seitenende: | 9 | Zusammenfassung: | A family of dimeric, peroxo-containing heteropolytungstates, [M(2)(O(2))(2)(XW(11)O(39))(2)](12-) [M = Zr(4+), X = Si (1), Ge (2); M = Hf(4+), X = Si (3)], have been synthesized by reacting ZrCl(4)/HfCl(4) with the respective monolacunary Keggin precursor [XW(11)O(39)](8-) (X=Si, Ge) in an aqueous acidic medium (pH 4.8). The isostructural polyanions 1-3 are composed of two (XW(11)O(39)) Keggin units encapsulating a central diperoxo-dimetal fragment {M(2)(O(2))(2)}(4+) (M=Zr(4+), Hf(4+)). Cyclic voltammetry and exhaustive electrolysis studies indicate fast reductive release of the peroxo ligands upon reduction of 1-3. Stoichiometric oxo-transfer studies from 1-3 to the substrate L-methionine were performed, and the reactions were monitored by (1)H NMR. |
ISSN: | 00201669 | DOI: | 10.1021/ic902203p |
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geprüft am 17.05.2024