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

第 13 族中性和阳离子金属磷菲 - 合成、结构和反应性

• 批准号: 466114454
• 负责人: Professor Dr. Stephan Schulz
• 金额: --
• 依托单位: Anorganische Chemie - AK Schulz
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/466114454?language=en
• 关键词: Neutral; cationic; Metallaphosphenes; Group; 13

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.

具有π键贡献的13/15族重元素化合物仍是一个科学课题。虽然近年来已经合成了B-N和Al-N化合物，并显示了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。在本研究项目中，我们希望发展一条合成具有π键贡献的中性均-和杂-金属磷杂菲L（X）MPM 'L（M，M' = Al，Ga In）以及相应阳离子物种[LMPML]+的通用路线。前期研究表明，M-P双键具有很高的反应活性，将用于小分子的键活化反应。在这些反应中，我们还将评估M-P双键（M = Al，Ga，In）的极性对反应性/选择性的影响。除了化学计量的键活化反应，我们还将尝试或首次使用金属磷烯催化反应，使用选定的底物。最后，我们希望使用二-和三取代的金属磷杂烯酮（LM（PCO）2，M（PCO）3）的合成迄今未知的二-和三金属磷杂苯（LM（PML 1）2，M（PML 1）3），这可能会显示出有趣的合作效应，在键活化反应。将进行量子化学计算以及原位1H和31 P 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理。