單芽氮異環碳烯之重元素相似物的性質及配位特性已經被研究了數十年,並 且在這方面有顯著的成果。然而,在單一分子中具有兩個以上的氮異環碳烯重元 素相似物卻是非常少見。因此,在本篇論文中,我們以合成具有高對稱性的多牙 氮異環碳烯重元素相似物為目標,其中包含了鍺烯、錫烯、r 及鉛烯,並對其做鑑 定及反應性的探討。在分子設計的部分,我們藉由立障極大的取代基,如:均三 甲苯和叔丁基,來穩定碳烯重元素相似物中的空軌域,並且以三亞苯作為分子骨 架來達成高對稱性分子的目的。鍺烯、錫烯、及鉛烯的合成,可以利用二價的鍺、 錫、鉛的前驅物,利用取代反應來獲得,並且以異核核磁共振光譜來證明其存在。 在矽烯的合成方面,我們先和成了四價的矽烷前驅物,之後再以強還原試劑將四 價矽還原成二價矽,但是在經過許多嘗試後,還是無法達到預期的結果。
Being the heavier analogues of N-heterocyclic carbene, the coordination chemistry of the so-called NHE (E = Si, Ge, Sn, Pb) have been investigated for decades. However, while significant progresses were made in poly-NHCs, molecules bearing multiple NHE units have only been reported few times. In this work, the syntheses of symmetrically N,N’-substituted tritopic metallylenes featuring a rigid molecular backbone will be presented. Tritopic NHSi precursors, dichlorosilanes, obtained from deprotonated hexa-(alkylamino)triphenylene and SiCl4 failed in generating tri-silylene from chemical reductions with K, KC8, and LiNp. On the other hand, reaction of deprotonated hexamine and ECl2 (E = Sn, Pb) gives the desired tritopic metallylenes, which can also be prepared from the reaction of hexamine and E[N(TMS)2]2 (E = Ge, Sn, Pb). The only exception is the reaction of hexa-(tert-butylamino)triphenylene and Sn[N(TMS)2]2 that yields the imine coordinated stannylene.
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