A Silsesquioxane-Based Diphosphinite Ligand: Synthesis, DFT Study, and Coordination Chemistry
A Silsesquioxane-Based Diphosphinite Ligand: Synthesis, DFT Study, and Coordination Chemistry
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基于倍半硅氧烷的二亚次膦酸酯配体：合成、DFT 研究和配位化学
DOI：
10.1021/om030522y
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发表时间：
2003
期刊：
影响因子：
2.8
通讯作者：
D. Vogt
中科院分区：
文献类型：
--
作者：
J. I. V. D. Vlugt;M. Fioroni;J. Ackerstaff;R. W. Hanssen;A. Mills;A. Spek;A. Meetsma;H. Abbenhuis;D. Vogt
不完全缩合的倍半硅氧烷二硅烷醇 (c-C5H9)7Si7O9(OH)2OSiMePh2 已被用作合成基于倍半硅氧烷骨架的二亚次膦酸酯配体 (c-C5H9)7Si7O9(OPPh2)2OSiMePh2 (1) 的主链。与黑硒反应，得到相应的硒化物(2)，31P NMR谱中JSe-P值为815Hz。 DFT 计算可以很好地了解两种模型化合物 CH3OPPh2 (3) 和 Ph2P(HSiOH)2OPH2 (4) 中 P 原子的电子密度。 Mulliken电荷分布显示硅氧基具有明显的吸电子效应，该硅氧基也存在于二次亚膦酸酯配体1中。化合物1与PdCl2(C6H5CN)2反应，得到钯配合物[PdCl2R(OPPh2)2](5)(R = (c-C5H9)7Si7O9OSiMePh2)。通过 1 与 PtCl2(cod) 的类似反应，可以分离出铂类似物 [PtCl2R(OPPh2)2] (6)。 Mo(CO)4(pip)2 (pip = 哌啶) 与 1 的等摩尔反应生成钼络合物 [Mo(CO)4R(OPPh2)...
The incompletely condensed silsesquioxane disilanol (c-C5H9)7Si7O9(OH)2OSiMePh2 has been used as a backbone for the synthesis of the diphosphinite ligand (c-C5H9)7Si7O9(OPPh2)2OSiMePh2 (1), based on a silsesquioxane framework. By reaction with black selenium, the corresponding selenide (2) was obtained, showing a JSe-P value of 815 Hz in the 31P NMR spectrum. DFT calculations established a good insight into the electron density of the P atoms present in the two model compounds CH3OPPh2 (3) and Ph2P(HSiOH)2OPH2 (4). The Mulliken charge distributions show a clear electron-withdrawing effect of the siloxy group, which is also present in diphosphinite ligand 1. By reaction of compound 1 with PdCl2(C6H5CN)2, the palladium complex [PdCl2R(OPPh2)2] (5) was obtained (R = (c-C5H9)7Si7O9OSiMePh2). From a similar reaction of 1 with PtCl2(cod), the platinum analogue [PtCl2R(OPPh2)2] (6) could be isolated. The equimolar reaction of Mo(CO)4(pip)2 (pip = piperidine) with 1 yielded the molybdenum complex [Mo(CO)4R(OPPh2)...