Versatile Phosphite Ligands Based on Silsesquioxane Backbones
Versatile Phosphite Ligands Based on Silsesquioxane Backbones
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基于倍半硅氧烷主链的多功能亚磷酸酯配体
DOI：
10.1002/adsc.200303186
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发表时间：
2004
影响因子：
5.4
通讯作者：
D. Vogt
中科院分区：
文献类型：
--
作者：
van der Vlugt;J. Ackerstaff;T. Dijkstra;A. Mills;H. Kooijman;A. Spek;A. Meetsma;Hcl Erik Abbenhuis;D. Vogt
使用倍半硅氧烷作为配体骨架用于合成具有3，3 ′-5，5 ′-四（叔丁基）-2，2 ′-二氧杂-1，1 ′-联苯取代基的新型亚磷酸酯化合物。以良好的产率制备单齿和双齿亚磷酸酯。采用两种类型的倍半硅氧烷作为起始材料。单亚磷酸酯I和单亚磷酸酯2由衍生自完全缩合的倍半硅氧烷骨架（c-C5 H9）（7）Si 7 O 12 SiOT 1的倍半氧化铊制备。从不完全缩合的单甲硅烷基化二硅烷醇（cC（5）H（9））（7）Si 7 O 9（OSiMePh 2）（OH）（2）开始合成二亚磷酸酯3。对于单亚磷酸酯2，相应的反式- [PtCl 2（2）]配合物4通过NMR光谱以及通过X射线晶体学表征，作为完全缩合的氧代官能化的倍半硅氧烷骨架的第一个实例。双齿配体3对Pd，Mo和Rh的配位进行了研究，无论是通过NMR光谱，以及通过X-射线晶体学。各种模式的协调被证明是可能的。测定了配合物trans-PdCl_2（3）]（5），cis-[Mo（CO）（4）（3）]（6）和双核配合物[{Rh（mu-Cl）（CO）}（2）（kappa（2）-3）]（7）的分子结构。在铑催化的I-辛烯加氢缩合反应中，这些新的纳米级磷配体获得了高活性，其转换频率高达6800 h（-1）。
Silsesquioxanes are employed as ligand backbones for the synthesis of novel phosphite compounds with 3,3'-5,5'-tetrakis(tert-butyl)-2,2'-di-oxa-1,1'-biphenyl substituents. Both mono- and bidentate phosphites are prepared in good yields. Two types of silsesquioxanes are employed as starting materials. The monophosphinite I and the monophosphite 2 are prepared from the thallium silsesquioxide derived from a completely condensed silsesquioxane framework (c-C5H9)(7)Si7O12SiOTl. The diphosphite 3 is synthesized starting with the incompletely condensed monosilylated disilanol (cC(5)H(9))(7)Si7O9(OSiMePh2)(OH)(2). For monophosphite 2, the corresponding trans- [PtCl2(2)] complex 4 is characterized by NMR spectroscopy as well as by Xray crystallography, as the first example of a completely condensed oxo-functionalized silsesquioxane framework. The coordination of the bidentate ligand 3 towards Pd, Mo and Rh is studied, both by NMR spectroscopy as well as by X-ray crystallography. Various modes of coordination are shown to be possible. The molecular structures for the complexes trans- [PdCl2(3)] (5), cis-[Mo(CO)(4)(3)] (6) and the dinuclear complex [{Rh( mu-Cl)(CO)}(2)(kappa(2)-3)] (7) have been determined. In the rhodium-catalyzed hydro-formylation of I-octene high activities, with turnover frequencies of up to 6800 h(-1), are obtained with these new nanosized phosphorus ligands.