6-peroxo-6-zirconium crown and its hafnium analogue embedded in a. triangular polyanion: [M(6)(O(2))(6)(OH)(6)(gamma-SiW(10)O(36))(3)](18) (M = zr, hf)

Autor(en): Bassil, Bassem S.
Mal, Sib Sankar
Dickman, Michael H.
Kortz, Ulrich
Oelrich, Holger
Walder, Lorenz 
Stichwörter: Chemistry; Chemistry, Multidisciplinary; COMPLEXES; CRYSTAL-STRUCTURE; DAWSON; MODELS; OXIDATION CATALYSIS; POLYOXOMETALATE; POLYOXOTUNGSTATES; SILICOTUNGSTATES; ZIRCONIUM(IV)
Erscheinungsdatum: 2008
Herausgeber: AMER CHEMICAL SOC
Journal: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volumen: 130
Ausgabe: 21
Startseite: 6696+
Zusammenfassung: 
We have synthesized and structurally characterized the unprecedented peroxo-zirconium(IV) containing [Zr(6)(O(2))(6)(OH)(6)(gamma-SiW(10)O(36))(3)](18-) (1). Polyanion 1 comprises a cyclic 6 -peroxo-6-zirconium core stabilized by three decatungstosilicate units. We have also prepared the isostructural hafnium(V). analogue [Hf(6)(O)(6)(OH)(6)(gamma-SiW(10)O(36))(3)](18-) (2). We investigated the acid/base and redox properties of 1 by UV-vis spectroscopy and electrochemistry studies. Polyanion 1 represents the first structurally characterized Zr-peroxo POM with side-on, bridging peroxo units. The simple, one-pot synthesis of 1 and 2 involving dropwise addition of aqueous hydrogen peroxide could represent a general procedure for incorporating peroxo groups into a large variety of transition metal and lanthanide containing POMs.
ISSN: 00027863
DOI: 10.1021/ja801424q

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