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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