Lanthanide complexes of the monovacant Dawson polyoxotungstate [α1-P2W17O61]10- as selective and recoverable Lewis acid catalysts
Lanthanide complexes of the monovacant Dawson polyoxotungstate [α1-P2W17O61]10- as selective and recoverable Lewis acid catalysts
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DOI：
10.1002/anie.200600364
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发表时间：
2006-01-01
影响因子：
16.6
通讯作者：
Malacria, Max
中科院分区：
文献类型：
--
作者：
Boglio, Cecile;Lemiere, Gilles;Malacria, Max
多金属氧酸盐 (POM) 是高氧化态早期过渡金属的一大族金属-氧簇，最常见的是 VV、MoVI 和 WVI。[1]它们作为电子受体或非常强的布朗斯台德酸（质子化形式）的固有化学特性使它们成为有机转化中的催化剂，[2]并且它们形成过氧配合物或作为高氧化态催化活性金属离子的载体的能力在氧化反应中特别有用。 [3] POM 的有机金属衍生物已被证明是加氢反应中的有效催化剂。[4]然而，据我们所知，迄今为止，尽管有许多可以解决的转化问题，但涉及 POM 的路易斯酸催化尚未见报道。我们想象单空位 POM 的镧系元素配合物（通常称为 Peacock-Weakley 型 [5, 6]），特别是 [α1-P2W17O61] 10À [7–18] 将是完成此类任务的良好候选者。其中一些化合物的稀土离子提供的发光和磁性特性已经被研究过。[19-21] Hill 和同事在 Keggin 衍生物中使用了铈 (iv) 的氧化特性
Polyoxometalates (POMs) are a large family of metal–oxygen clusters of the early transition metals in high oxidation states, most commonly VV, MoVI, and WVI.[1] Their intrinsic chemical properties as electron acceptors or as very strong Brønsted acids (in their protonated form) makes them catalysts in organic transformations,[2] and their ability to form peroxo complexes or to serve as a support for catalytically active metal ions in a high oxidation state is particularly useful in oxidation reactions.[3] Organometallic derivatives of POMs have proven to be effective catalysts in hydrogenation reactions.[4]To the best of our knowledge, however, no Lewis acid catalysis involving POMs has been reported so far, despite the wide array of transformations that could be addressed. We imagined that lanthanide complexes of monovacant POMs—often called Peacock–Weakley type [5, 6]—and in particular of [α1-P2W17O61] 10À [7–18] would be good candidates for such a task. Some of these compounds have already been studied for their luminescence and magnetic properties provided by the lanthanide ions.[19–21] Hill and co-workers have used the oxidant properties of cerium (iv) in the Keggin derivative