Silylium Ion/Phosphane Lewis Pairs
Silylium Ion/Phosphane Lewis Pairs
复制标题
硅离子/磷烷路易斯对
DOI：
10.1021/om400559x
复制
发表时间：
2013
期刊：
影响因子：
2.8
通讯作者：
T. Müller
中科院分区：
文献类型：
--
作者：
Matti Reissmann;A. Schäfer;Sebastian T. Jung;T. Müller
研究了一系列硅离子/膦路易斯对的反应性。三芳基硅硼酸 4[B(C6F5)4] 与位阻膦 2 形成中等稳定性的受挫路易斯对 (FLP)。其中一些 FLP 能够在环境条件下裂解二氢。大体积的三烷基膦与三芳基硅鎓离子的组合可用于以甲硅烷基鏻离子12的形式封存CO2。通过硅鎓离子/膦路易斯对反应活化分子氢的能力由热力学和空间因素决定。对于给定的硅离子，增加磷烷的质子亲和力和增加空间位阻被证明是有益的。然而，过多的空间位阻会导致硅/膦路易斯对的二氢分裂活性的破坏。
The reactivity of a series of silylium ion/phosphane Lewis pairs was studied. Triarylsilylium borates 4[B(C6F5)4] form frustrated Lewis pairs (FLPs) of moderate stability with sterically hindered phosphanes 2. Some of these FLPs are able to cleave dihydrogen under ambient conditions. The combination of bulky trialkylphosphanes with triarylsilylium ions can be used to sequester CO2 in the form of silylacylphosphonium ions 12. The ability to activate molecular hydrogen by reaction of silylium ion/phosphane Lewis pairs is dominated by thermodynamic and steric factors. For a given silylium ion increasing proton affinity and increasing steric hindrance of the phosphane proved to be beneficial. Nevertheless, excessive steric hindrance leads to a breakdown of the dihydrogen-splitting activity of a silylium/phosphane Lewis pair.
影响因子：
2.8
作者：
Schaefer, Andre;Reissmann, Matti;Mueller, Thomas
通讯作者：
Mueller, Thomas