Synthesis of Al(I)-based Frustrated Lewis Pairs and Reactivity in Activation of Small Nitrogen-containing Molecules

合成新型Al（I）化合物及其衍生的阻挫刘易斯对（FLP），最终目的是将其应用于小分子活化。特别是它们对作为二氮同系物的含氮小分子的行为将引起人们的兴趣。在这里，空间要求高的刘易斯酸的帮助，通过在受抑的刘易斯对之间捕获相应的底物，从而促进NN键的断裂和其他小分子的攻击，来创造协同的推拉环境是至关重要的。缺电子Al（I）中心的稳定化通过引入单阴离子多齿（双齿Y = L和钳形Y = L2，Y =阴离子供体，L =中性供体）配体来解决，所述单阴离子多齿配体具有实质性空间需求以提供动力学稳定化，而电子稳定化通过强供体部分来实现。通过在空间体积以及供体和受体性质方面仔细调整配体系统，预期Al（I）中心的不同反应性。这种高活性和刘易斯碱性或两亲性化合物被认为显示出前所未有的和迷人的新的反应活性。

The synthesis of novel Al(I) compounds and derived frustrated Lewis pairs (FLP) is addressed with the ultimate goal to apply them in small molecule activation. Especially their behaviour towards small nitrogen-containing molecules acting as dinitrogen congeners will be of interest. Here, the aid of sterically demanding Lewis acids to create a synergistic push-pull environment by capturing the respective substrate in between the frustrated Lewis pair, thereby facilitating NN bond scissions and attacks of other small molecules is crucial. Stabilization of the electron deficient Al(I) centers is tackled by the introduction of monoanionic multidentate (bidentate Y∩L and pincer Y∩L2, Y = anionic donor, L = neutral donor) ligands with substantial steric demand to provide kinetic stabilization, whereas electronic stabilization is implemented by strong donor moieties. By careful tuning of the ligand system in terms of steric bulk, as well as donor and acceptor properties, different reactivities of the Al(I) center are expected. Such highly reactive and Lewis basic or ambiphilic compounds are presumed to show unprecedented and fascinating new reactivities.