6-Peroxo-6-zirconium crown and its hafnium analogue embedded in a triangular polyanion: [M6(O2)6(OH)6(gamma-SiW10O36)3]18- (M = Zr, Hf)

Bassem S Bassil; Sib Sankar Mal; Michael H Dickman; Ulrich Kortz; Holger Oelrich; Lorenz Walder

doi:10.1021/ja801424q

6-Peroxo-6-zirconium crown and its hafnium analogue embedded in a triangular polyanion: [M6(O2)6(OH)6(gamma-SiW10O36)3]18- (M = Zr, Hf)

J Am Chem Soc. 2008 May 28;130(21):6696-7. doi: 10.1021/ja801424q. Epub 2008 May 1.

Authors

Bassem S Bassil¹, Sib Sankar Mal, Michael H Dickman, Ulrich Kortz, Holger Oelrich, Lorenz Walder

Affiliation

¹ School of Engineering and Science, Jacobs University, P.O. Box 750561, 28725 Bremen, Germany.

PMID: 18447356
DOI: 10.1021/ja801424q

Abstract

We have synthesized and structurally characterized the unprecedented peroxo-zirconium(IV) containing [Zr6(O2)6(OH)6(gamma-SiW10O36)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(IV) analogue [Hf6(O2)6(OH)6(gamma-SiW10O36)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.