Neutral and cationic Metallaphosphenes of Group 13 - Synthesis, Structure and Reactivity

有π键贡献的重元素的13/15族化合物仍然是一个科学任务。虽然近年来已经合成了B-N和Al-N化合物，并显示出它们有趣的化学反应性，但较重元素的类似化合物仍然很少。在本课题中，我们希望开发一种具有π键贡献的中性homo-和杂双金属金属硫代烯L(X)MPM'L （M， M' = Al, Ga In）以及相应阳离子物种[LMPML]+的合成方法。初步研究表明，M-P双键具有较高的反应活性，可用于小分子的键激活反应。在这些反应中，我们还将评估M - p双键极性（M = Al, Ga, In）对反应性/选择性的影响。除了化学计量键激活反应外，我们还将尝试或首次使用金属磷烯在选定的底物上进行催化反应。最后，我们想用二取代和三取代金属磷烯烯(LM（PCO)2， M(PCO)3）合成迄今未知的二取代和三取代金属磷烯(LM(PML1)2， M(PML1)3)，它们可能在键激活反应中表现出有趣的协同效应。将进行量子化学计算以及原位1H和31P NMR光谱研究，以更深入地了解化合物的电子结构，并确定可能的反应机制。

Group 13/15 compounds of the heavier elements with π-bonding contribution are still a scientific task. While B–N and Al–N compounds have been synthesized and their interesting chemical reactivity has been shown in recent years, analogous compounds of the heavier elements are still rare. In this research project we want to develop a general route for the synthesis of neutral homo- and heterobimetallic metallaphosphenes L(X)MPM'L (M, M' = Al, Ga In) with π-bonding contribution as well as the corresponding cationic species [LMPML]+. The promising high reactivity of the M–P double bond, which was demonstrated in preliminary studies, will be used for bond activation reactions of small molecules. In these reactions, we will also evaluate the influence of the polarity of the M–P double bond (M = Al, Ga, In) on the reactivity / selectivity. Aside from stoichiometric bond activation reactions, we will also try or the first time to use metallaphosphenes for catalytic reactions using selected substrates. Finally, we want to use di- and trisubstituted metallaphosphaketenes (LM(PCO)2, M(PCO)3) for the synthesis of so far unknown di- and trimetallaphosphenes (LM(PML1)2, M(PML1)3), which may show interesting cooperative effects in bond activation reactions. Quantum chemical calculations as well as in situ 1H and 31P NMR spectroscopic studies will be performed to get deeper insights into the electronic structure of the compounds as well as to identify possible reaction mechanism.