Kramer Nina, Wadepohl Hubert, Greb Lutz
Anorganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 275, 69120 Heidelberg, Germany.
Chem Commun (Camb). 2019 Jul 2;55(54):7764-7767. doi: 10.1039/c9cc03625c.
Although several strategies for the stabilization of silylium ions have been established, "π-stabilization" with directly attached π-donor heteroatoms at silicon has not been developed yet. Hydride abstraction from (Me2N)3SiH generates dicationic [(Me2N)3Si+]2 in solution and in the solid state - constituting the dimer of an elusive silaguanidinium ion. This compound can be synthesized on a gram scale and is compatible with common organic solvents. However, it readily undergoes spontaneous electrophilic silylation of electron-rich aromatic compounds or initiates a catalytic hydro-defluorination reaction.
尽管已经建立了几种稳定硅鎓离子的策略，但尚未开发出在硅上直接连接π供体杂原子的“π稳定化”方法。从(Me2N)3SiH中提取氢化物会在溶液和固态中生成双阳离子[(Me2N)3Si+]2，它构成了一种难以捉摸的硅胍鎓离子的二聚体。这种化合物可以以克级规模合成，并且与常见的有机溶剂兼容。然而，它很容易对富电子芳香化合物进行自发的亲电硅烷化反应，或引发催化加氢脱氟反应。
