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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