Bassil Bassem S, Mal Sib Sankar, Dickman Michael H, Kortz Ulrich, Oelrich Holger, Walder Lorenz
School of Engineering and Science, Jacobs University, P.O. Box 750561, 28725 Bremen, Germany.
J Am Chem Soc. 2008 May 28;130(21):6696-7. doi: 10.1021/ja801424q. Epub 2008 May 1.
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.
我们已经合成并通过结构表征了前所未有的含过氧锆（IV）的[Zr6(O2)6(OH)6(γ-SiW10O36)3]18-（1）。聚阴离子1包含一个由三个十钨硅酸单元稳定的环状六过氧-六锆核。我们还制备了同结构的铪（IV）类似物[Hf6(O2)6(OH)6(γ-SiW10O36)3]18-（2）。我们通过紫外可见光谱和电化学研究研究了1的酸碱和氧化还原性质。聚阴离子1代表了第一个具有侧基桥连过氧单元且结构已表征的锆过氧多金属氧酸盐。1和2的简单一锅法合成涉及逐滴加入过氧化氢水溶液，这可能是将过氧基团引入多种含过渡金属和镧系元素的多金属氧酸盐的通用方法。
