Bisphosphano Silylenes

在这个项目中，我们提出了一种新型硅烯的合成途径，其中取代基通过P（III）原子连接到中心的低价硅原子上。这种设置很可能引起一种独特的电子情况，对硅烯装置的电子激发和反应性有影响。磷原子的位置很理想，可以作为探针，用31P-NMR谱反映Si和P之间的键合情况和相互作用。此外，将磷原子与1,1'-二茂铁单元桥接是一种很有吸引力的方法，可以使茂金属的铁原子靠近硅烯单元，从而研究这些中心之间的潜在相互作用。对于基于二茂铁的碳烯，已经出现了不寻常的键合情况和对小分子的反应模式，这将扩展到所提出的硅烯。二茂铁部分的显著氧化还原特性应该非常适合于研究初始铁氧化时电子从>P-Si-P<单元向铁中心的转移。最终，这项基础研究的结果可能为发现新的反应性和长期开发低能激发材料开辟道路。

In this project we propose a synthetic access to a novel type of silylenes in which the substituents are connected via P(III) atoms to the central low valent silicon atom. This setting is likely to invoke a unique electronic situation with implications for electronic excitation and reactivity of the silylene unit. The phosphorus atoms are ideally located to serve as probe reflecting the bonding situation and interaction between Si and P using 31P-NMR spectroscopy. Moreover, bridging the phosphorus atoms with a 1,1'-ferrocenylene unit, is an attractive way to get the iron atom of the metallocene in proximity to the silylene unit in order to study potential interactions between these centers. For ferrocene based carbenes unusual bonding situations and reactivity patterns towards small molecules have emerged, which shall be extended to the proposed silylenes. The remarkable redox properties of the ferrocene moiety should be well suited to investigate an electron transfer from the >P-Si-P< unit to the iron center upon initial iron oxidation. Ultimately, the results of this fundamental research may open the way to the discovery of novel reactivities and the development of low-energy excitation materials on a long term base.