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.

组13/15组具有π键作用的较重元素的化合物仍然是一项科学任务。虽然B – N和Al -N化合物已合成，并且近年来已经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见。在该研究项目中，我们希望开发一条一般途径，用于合成中性和杂物金属圈L（x）mpm'l（m，m'= al，ga in），具有π键的贡献以及相应的阳离子物种[lmpml]+。在初步研究中证明的MP双键的有希望的高反应性将用于小分子的键激活反应。在这些反应中，我们还将评估MP双键（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，我们还将尝试使用选定的底物使用映圈元素进行催化反应。最后，我们希望使用DI-和TrisubSTTETSET的荟萃磷酸（LM（PCO）2，M（PCO）3）进行迄今未知的二磷酸和三翼圈（LM（PML1）2，M（PML1）3）的合成，这可能在键盘激活反应中显示出有趣的合作作用。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。