Functionalization of Polyoxometalates : Achievements and Perspectives
Functionalization of Polyoxometalates : Achievements and Perspectives
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DOI：
10.1007/0-306-47625-8_3
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发表时间：
2001
期刊：
影响因子：
--
通讯作者：
A. Proust;R. Villanneau
中科院分区：
文献类型：
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作者：
A. Proust;R. Villanneau
这一贡献将集中在多键配体的多金属氧酸盐功能化，特别是亚硝基，亚胺和环戊二烯基配体。第一部分将定义不同合成方法的范围，即具有Mo=O键的[2+2]反应，通过a-氢的缩合型反应，以及通过置换不稳定配体的自组装反应，例如。卤化物或溶剂，从适当的金属配合物。选定的例子将提出和最终的复杂性，例如。水解或还原，将被讨论。将特别注意磷酰化物对多氧钼酸盐的反应性，这与磷酰亚胺的反应性形成对比。第二部分将显示功能化可能提供母体阴离子的电子性质微调。代表性的例子包括表面氧原子的活化，如lindqvist型阴离子的甲基化所证明的，以及特定化合物的稳定，如。[M4O13(OMe)4{Mo(NO)}]3−（M = Mo或W）和[Mo10O31−x(OMe)x(NO)]z−，它们表现出自己有趣的化学性质。此外，核磁共振和电化学数据强调了附着的配体和多金属氧酸酯部分之间的一些电子通信：系列[Mo6O18(NC6H4 - p - X)]2 -提供了一个明显的例子，其中95mo和14n的化学位移和还原电位与取代基的Hammett常数相关。最后一部分将讨论环戊二烯基衍生物的合成及其在设计用于各种应用的强相互作用双极体系中的潜力，例如。光致变色或电致变色材料及传感器。
This contribution will focus on the functionalization of polyoxometalates with multiply bonded ligands, notably nitrosyl, imido and cyclopentadienyl ligands. The first part will define the scope of the different synthetic methodologies,i.e.net [2+2] reactions with Mo=O bonds, condensation-type reactionsviaa-hydrogen, and self-assembly reactionsviathe displacement of labile ligands,e.g.halide or solvent, from appropriate metal complexes. Selected examples will be presented and the eventual complications,e.g.hydrolysis or reduction, will be discussed. Special attention will be paid to the reactivity of phosphonium ylides towards polyoxomolybdates which contrasts that of phosphinimines.The second part will show that functionalization may provide fine tuning of the electronic properties of the parent anion. Representative examples include the activation of surface oxygen atoms, as demonstrated by methylation of Lindqvist-type anions, and the stabilization of specific compounds,e.g.[M4O13(OMe)4{Mo(NO)}]3−(M = Mo or W), and [Mo10O31−x(OMe)x(NO)]z−, which display their own, interesting, chemistry. Furthermore, NMR and electrochemical data underscore some electronic communication between the attached ligand and the polyoxometalate moiety: a clear example is provided by the series [Mo6O18(NC6H4−p−X)]2−where95Mo and14N chemical shifts and reduction potentials correlate with the Hammett constant of the substituent.The last part will deal with the synthesis of cyclopentadienyl derivatives and their potential in the design of strongly interacting bipolar systems for various applications,e.g.photochromic or electrochromic material, and sensors.