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Donor-stabilized monomeric pentelylalanes and gallanes: beyond the steric bulk

供体稳定的单体戊二烷和镓烷：超越空间体积

基本信息

批准号：
323408236
负责人：
Professor Dr. Manfred Scheer
金额：
--
依托单位：
Institut für Anorganische Chemie
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2017
资助国家：
德国
起止时间：
2016-12-31 至 2020-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/323408236?language=en
关键词：
Donor stabilized monomeric pentelylalanes gallanes

项目摘要

During the last decade mixed Group 13/15 compounds attracted significant attention as precursors for functional materials, inorganic polymers or as hydrogen storage materials. Current studies focused in particular on N/B- and P/B-systems and although synthetic procedures for the heavier analogs have been developed, they remain underrepresented and such derivatives still bear bulky organo-substituents. The parent compounds of the type H2EMH2 (M = Group 13 element, E = Group 15 element) are isoelectronic with ethane, have not been isolated yet and were only be described by computational studies. In this respect, the Scheer group succeeded in the isolation of the monomeric parent compound of the phosphanylalanes and -gallanes (OC)5W·H2PMH2·NMe3 (M = Al, Ga) by applying Lewis acid(LA)/base(LB) stabilization and achieved the first controlled oligomerization reactions of those compounds. The present project is focused on the fine tuning of the electronic and steric properties of the starting materials and the reaction conditions (temperature, solvent and others) to control the H2 elimination process for such compounds with the ultimate goal to obtain the most condensed, H-free cage compounds and mixed Group 13/15 chain composites. The selective substitution by special organic moieties on the pentel atom will lead to reactive precursors for the fabrication of novel soluble, mixed Group 13/15 oligomeric/polymeric materials. Furthermore, the synthesis of the only donor-stabilized (LB) compounds of the type H2EMH2·LB (E = P, As, Sb; M = Al, Ga) is a central goal of the project via a novel salt metathesis route from LB·MH2I or by a LA abstraction method from LA·H2PMH2·LB (M = Al, Ga) by appropriate LBs. Strong donors like carbenes with a high steric demand are promising LBs to generate the only by a LB stabilized parent compounds for the first time. Moreover, the yet unknown only by a LA stabilized parent compound of the type LA·H2PMH2 will be synthesized within this project. The research on these different types of compounds will be accompanied and complemented by extensive gas phase and thermal investigations as well as by additionally DFT calculations. In particular, compounds of the type H2PMH2·LB (M = Al, Ga), with LBs with negligible volatility - like sterically congested N-heterocyclic carbenes or cyclic(alkyl)(amino)carbenes - are expected to liberate H2PMH2 into the gas phase or into the argon matrix and allow its detection for the very first time.

在过去十年中，混合的13/15族化合物作为功能材料、无机聚合物或储氢材料的前体引起了极大的关注。目前的研究主要集中在N/B-和P/B-系统上，虽然已经开发了较重类似物的合成方法，但它们的代表性仍然不足，而且这些衍生物仍然含有大量的有机取代基。H2EMH2型的母体化合物（M =第13族元素，E =第15族元素）与乙烷是等电子的，还没有被分离出来，只能通过计算研究来描述。在这方面，Scheer团队通过Lewis酸(LA)/碱（LB）稳定化，成功地分离出了磷酰三烷和-没食子烷（OC）的单体母体化合物5W·H2PMH2·NMe3 (M = Al, Ga)，并首次实现了这些化合物的可控寡聚反应。本项目主要通过对起始原料的电子和位阻性质以及反应条件（温度、溶剂等）的精细调整来控制该类化合物的H2消除过程，最终获得最凝聚、无h的笼状化合物和混合的13/15基团链复合材料。戊二原子上特殊有机基团的选择性取代将产生反应性前体，用于制备新型可溶、混合的13/15族低聚/聚合物材料。此外，通过LB·MH2I的新型盐复分解路线或LA·H2PMH2·LB （M = Al, Ga）的LA提取方法合成H2EMH2·LB （E = P, As, Sb; M = Al, Ga）类型的唯一供体稳定（LB）化合物是该项目的中心目标。强供体如高立体需求的carbenes有望首次生成唯一由LB稳定的母体化合物。此外，该项目还将合成LA·H2PMH2型的LA·H2PMH2型的未知母化合物。对这些不同类型化合物的研究将伴随并补充广泛的气相和热研究以及额外的DFT计算。特别是，H2PMH2·LB （M = Al, Ga）类型的化合物，具有可忽略挥发性的LBs -如立体密集的n -杂环碳烯或环（烷基）（氨基）碳烯-有望将H2PMH2释放到气相或氩气基体中，并首次被检测到。