Multiply Lewis-acidic and metallophilic receptor systems with trisilacyclohexane skeletons

将路易斯酸性和亲金属受体系统与三硅杂环己烷骨架相乘

• 批准号: 313483887
• 负责人: Professor Dr. Norbert W. Mitzel
• 金额: --
• 依托单位: Arbeitsgruppe Anorganische Chemie und Strukturchemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2020-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/313483887?language=en
• 关键词: Multiply; Lewis; acidic; metallophilic; receptor

Specific chemical functionality can be achieved by purposeful selection of functions and their defined spatial positioning. This principle is realized in nature in many ways, for example in enzymes and chemists use it when designing molecular catalysts. Typically, donor functions or hydrogen bridging units are made use of, while the arrangement of Lewis-acidic receptors is much less common. However, such an approach opens up the possibility for detecting and complexing anions or Lewis bases and thus to change their properties and reactivities. The aim of this project is the synthesis and utilization of new systems with multiple spatially aligned Lewis-acidic or metallophilic receptor functions. In previous work we have shown that trisilacyclohexane frameworks substituted with three alkyne groups represent a class of molecules that possess all prerequisites for the construction of the desired target systems: good preparative accessibility, absence of competing Lewis base functionalities and facile functionalization by a number of established reactions. In this project several classes of trialkyne-trisilacyclohexanes are to be terminally metalated with metal alkyls via alkane elimination reactions, or metal functions are to be added via hydrometalation reactions to the alkyne groups. In this way, groups like R2Al, Cl2Ga and R2Ga or electronegatively substituted boryl and silyl groups such as BR2 and SiR3 (R = F, Cl, C2F5, C6F5, C6F3(CF3)2, etc.) but also other metal atoms such as gold and mercury will be attached to the rigid frameworks. The former serve to construct molecular skeletons with the possibility of substrate recognition via Lewis acid-base interactions, the latter make use of dispersive driven d10-d10 interactions. The goal is to learn constructing tailor-made receptors and to use them for selective recognition and modification of chemical and physical properties of Lewis basic or metallophilic substrates. Further application aspects of this chemistry concern the examination of chelating Lewis acids in the chemistry of frustrated Lewis pairs and to try a new approach in designing super-Lewis-acids in the form of metal-adadamantane compounds with pyramidal coordination environments of their Group 13 elements.

特定的化学功能可以通过有目的的功能及其定义的空间定位来实现。该原理在本质上是在许多方面实现的，例如在设计分子催化剂时在酶中使用它。通常，使用供体功能或氢桥接单元，而路易斯 - 酸性受体的排列却不那么普遍。但是，这种方法为检测和络合阴离子或刘易斯碱的可能性开辟了可能性，从而改变了它们的性质和反应性。该项目的目的是合成和利用具有多个空间比对的刘易斯 - 酸性或金属志受体功能的新系统。在先前的工作中，我们已经表明，用三个藻类组代替的三曲己烷框架代表了一类分子，这些分子具有建造所需目标系统的所有先决条件：良好的准备式可访问性，缺乏竞争性的刘易斯基础功能和既有既定反应的竞争性基础功能。在该项目中，几种类型的试验 - 三乙酰己烯剂应通过烷基消除反应将金属烷基终止金属化，否则将通过对烷基基团的水文测定反应添加金属功能。这样，诸如R2AL，CL2GA和R2GA或诸如BR2和SIR3之类的甲硅烷基类（R = F，Cl，C2F5，C6F5，C6F5，CF3（CF3）2等）等组等组，以及其他金属原子，例如金和Mercury等其他金属原子。前者用来构建具有通过路易斯酸碱相互作用底物识别的分子骨骼，后者利用了分散驱动的D10-D10相互作用。目的是学习构造量身定制的受体，并将其用于选择性识别和修改刘易斯碱性或金属粒子底物的化学和物理性质。这种化学的进一步应用方面涉及挫折的刘易斯对化学中螯合刘易斯酸的检查，并尝试以金属 - 阿达曼坦烷化合物的形式设计新方法，并具有其组13个元素的金字塔配位环境。