The main group element chemistry of polypnictogen complexes

聚光原配合物的主族元素化学

• 批准号: 470309834
• 负责人: Professor Dr. Peter Roesky
• 金额: --
• 依托单位: Institut für Anorganische Chemie (aoc)
• 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/470309834?language=en
• 关键词: main; group; element; chemistry; polypnictogen

In recent years, the development of new methods to convert white phosphorus (P4) into higher-value products has increased significantly. As an alternative to the use of the reactive P4 molecules as P source, the utilization of metal-stabilized polyphosphide-based systems is an elegant approach. What is more, the heavier homologs of phosphorus, i.e. arsenic and antimony, are, in their elementary form, either too unreactive or extremely difficult to handle so that their integration into organometallic compounds is the better choice. In our preliminary work, we were mainly focused on the targeted functionalization of [Cp*Fe(P5)] with reactive compounds of the main groups II-IV. Here, [Cp*Fe(P5)] served as an air-stable polyphosphorus source. In our investigations, we succeeded in achieving selective substitutions of the P atoms, ring expansions or insertion reactions and rearrangement reactions. Within the scope of this project, we intend to significantly expand the spectrum of pnictogen transition metal complexes as starting compounds and address the following research topics: a) in the field of phosphorus chemistry, we want to investigate as to what extent the substitution or ring expansion reactions observed so far can be generalized and systematized beyond [Cp*Fe(P5)]; b) the spectrum of ring and cage compounds will be extended to the heavy pnictogens and, here in particular, to arsenic in order to obtain fundamental reaction pathways; c) the following reaction types will be investigated in order to enable targeted syntheses in the future: ring or cage expansions, ring or cage contractions, rearrangements; d) in a rather risky work package, we will try to detach the pnictogen ligands from the metal after functionalization to access new systems composed of mixed main group elements.

近年来，将白磷（P4）转化为更高价值产品的新方法的开发显着增加。作为使用反应性 P4 分子作为磷源的替代方案，使用金属稳定的多磷化物基系统是一种优雅的方法。更重要的是，磷的较重同系物，即砷和锑，其单质形式要么太不活泼，要么极难处理，因此将它们整合到有机金属化合物中是更好的选择。在我们的前期工作中，我们主要关注用II-IV主族的反应性化合物对[Cp*Fe(P5)]进行靶向官能化。在这里，[Cp*Fe(P5)] 充当空气稳定的多磷源。在我们的研究中，我们成功实现了 P 原子的选择性取代、扩环或插入反应以及重排反应。在该项目的范围内，我们打算显着扩展磷元素过渡金属配合物作为起始化合物的范围，并解决以下研究主题：a）在磷化学领域，我们希望研究迄今为止观察到的取代或扩环反应在多大程度上可以推广和系统化，超越[Cp * Fe（P5）]； b) 环和笼化合物的谱将扩展到重磷元素，特别是砷，以获得基本的反应途径； c) 将研究以下反应类型，以便将来实现目标合成：环或笼扩张、环或笼收缩、重排； d）在一个相当危险的工作包中，我们将尝试在功能化后将磷元素配体与金属分离，以获得由混合主族元素组成的新系统。