Spirk Stefan, Nieger Martin, Belaj Ferdinand, Pietschnig Rudolf
Karl-Franzens-Universität, Institut für Chemie, Schuberststrasse 1, A-8010, Graz, Austria.
Dalton Trans. 2009 Jan 7(1):163-7. doi: 10.1039/b812974f. Epub 2008 Oct 23.
The formation of t-butyl substituted polyhedral silsesquioxanes (POSS) starting from the corresponding silanetriol is reported. Several intermediates involved in this complex condensation process could be identified spectroscopically. In addition, the initial condensation intermediate t-Bu(2)Si(2)O(OH)(4), as well as t-Bu(6)Si(6)O(9) and t-Bu(7)Si(7)O(9)(OH)(3), could be characterized by X-ray crystallography. Owing to the high crystal quality it was possible to experimentally determine the geometric parameters of the unusual cyclic hydrogen bond network in a dimeric POSS trisilanol for the first time. Furthermore, we investigated the structural changes concomitant with dimer formation/dissociation of the t-butyl substituted POSS trisilanol and its methyl analogue.
报道了从相应的硅三醇出发合成叔丁基取代的多面体倍半硅氧烷（POSS）的过程。通过光谱学方法可以鉴定出参与这一复杂缩合过程的几种中间体。此外，初始缩合中间体叔丁基二硅四醇（t-Bu(2)Si(2)O(OH)(4)）以及叔丁基六硅九醇（t-Bu(6)Si(6)O(9)）和叔丁基七硅九醇三羟基化物（t-Bu(7)Si(7)O(9)(OH)(3)）可以通过X射线晶体学进行表征。由于晶体质量高，首次通过实验确定了二聚体POSS三硅醇中异常环状氢键网络的几何参数。此外，我们还研究了叔丁基取代的POSS三硅醇及其甲基类似物在二聚体形成/解离过程中伴随的结构变化。
