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.

在过去的十年中，混合组13/15种化合物作为功能材料，无机聚合物或作为氢储存材料的前体引起了极大的关注。目前的研究特别针对N/B和P/B系统，尽管已经开发了较重的类似物的合成程序，但它们的代表性不足，并且这些衍生物仍然具有庞大的有机润滑剂。类型H2EMH2的母体化合物（M =组13元素，E =第15组元素）是等值的，尚未隔离，仅通过计算研究来描述。在这方面，Scheer组成功地隔离了磷酸烷烷烷和-Gallanes（OC）5W·H2PMH2·Nme3（M = Al，Ga），通过施加Lewis Acid（LA）/碱（LB）稳定性并实现了这些首次控制的元素化反应。本项目的重点是对起始材料的电子和空间特性的微调以及反应条件（温度，溶剂和其他），以控制具有最终目标的此类化合物的H2发射过程，以获得最终的无H-FROM笼子化合物和混合组13/15链组成。在五特定原子上通过特殊有机部分的选择性取代将导致制造新型固体混合组13/15低聚/聚合物材料的反应性前体。此外，H2EMH2·Lb型的唯一易位（LB）化合物的合成（E = P，AS，SB; M = Al，GA）是该项目的核心目标，这是通过LB·MH2I或La la abtraction方法或通过La·H2PPMH 2PMH 2PMH2PMH（MH2PMH2PMH）的新型盐分化途径（MH2I）（MH2I）的核心目标。诸如较高空间需求的Carbones之类的强大供体承诺首次通过LB稳定的父型化合物产生磅。此外，仅在该项目中合成了LA·H2PMH2类型的LA稳定母体化合物。对这些不同类型化合物的研究将通过广泛的气相和热量研究以及通过DFT计算来完成并完成。特别是，H2PMH2·Lb型的化合物（M = Al，GA），具有可忽略的波动性的LB-例如在空间上充血的N-杂环碳或环状（烷基）（氨基）Carbones-可以将H2PMH2释放到GAS或ARGON Matrix中，以便将其允许使用，并将其允许允许使用量很高，并允许其允许的距离，并将其最初允许允许，并将其最初允许使用。