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Generation of Silyl Cations by Hydroalumination Reactions

通过铝氢化反应生成甲硅烷基阳离子

基本信息

批准号：
82408704
负责人：
Professor Dr. Werner Uhl
金额：
--
依托单位：
Institut für Anorganische und Analytische Chemie
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2008
资助国家：
德国
起止时间：
2007-12-31 至 2017-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/82408704?language=en
关键词：
Generation Silyl Cations Hydroalumination Reactions

项目摘要

In the first period of this project we synthesized highly functionalized silicon and germanium compounds which had in one molecule Lewis basic donor atoms (X) bound to the group 14 element and Lewis acidic acceptor atoms (Al, Ga) in beta-position. Intramolecular interactions between the opposite functionalities yielded adducts with the concomitant activation of the E-X bonds. Complete transfer of the groups X to the aluminum and gallium atoms and cleavage of the E-X bonds may result in the formation of compounds with silyl or germyl cations which due to their zwitterionic nature should be soluble in non-polar organic solvents. The unique structures and reactivity of cations of this type based on separate ions initiated intense current research activities. In our compounds X represents nitrogen or chlorine atoms and the alpha-carbon atoms of alkynes. The activated alkynes gave an interesting rearrangement to yield sila- or germacyclobutenes which showed a remarkable fluorescent behavior. A first silyl cation may be formed as an intermediate in an unsymmetric dyotropic rearrangement. These compounds with activated Si-X or Ge-X bonds represent the first successful step for the synthesis of our target molecules, and we have learned to synthesize a large variety of compounds with E-X bond activation. These results clearly help to develop a reasonable strategy for our future work and the generation of cationic species. Complete cleavage of the E-X bond may be favored by the presence of electron donating substituents bound to silicon or germanium atoms, the modification of the leaving groups with respect to their hard- or softness and an increased acceptor strength of the aluminum or gallium atoms which may be achieved by electron withdrawing groups. The activated compounds obtained so far show a unique reactivity which resembles that one of the famous and intensely investigated Frustrated Lewis Pairs and may make an important contribution to the transition-metal-free activation of organic and inorganic substrates. Insertion reactions into the activated Si-X and Ge-X bonds or substituent exchange reactions are facilitated.

在这个项目的第一个阶段，我们合成了高度功能化的硅和锗化合物，它们在一个分子中有Lewis碱性给体原子(X)结合到14族元素上，Lewis酸性受体原子（Al, Ga）在β位置上。相反官能团之间的分子内相互作用产生加合物，同时激活E-X键。基团X完全转移到铝和镓原子上以及E-X键的断裂可能会形成具有硅基或根基阳离子的化合物，由于它们的两性离子性质，它们应该可溶于非极性有机溶剂。这种基于分离离子的阳离子的独特结构和反应性引发了当前激烈的研究活动。在我们的化合物中，X代表氮原子或氯原子和炔的碳原子。活化的炔烃进行了有趣的重排，生成了具有显著荧光特性的硅环丁烯或生环丁烯。第一硅基阳离子可以在不对称各向异性重排中作为中间体形成。这些具有活化Si-X或Ge-X键的化合物代表了我们目标分子合成成功的第一步，我们已经学会了合成各种具有E-X键活化的化合物。这些结果显然有助于为我们未来的工作和阳离子物种的产生制定合理的策略。与硅或锗原子结合的供电子取代基的存在、离去基相对于其硬度或柔软度的修饰以及铝或镓原子的受体强度的增加（可通过吸电子基团实现）可能有利于E-X键的完全裂解。目前获得的活性化合物显示出独特的反应活性，类似于著名的和被广泛研究的路易斯配对，可能对有机和无机底物的无过渡金属活化做出重要贡献。激活的Si-X和Ge-X键的插入反应或取代基交换反应被促进。

项目成果

期刊论文数量（10）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Silicon-Halogen Bond Activation in Mixed Si/Al Compounds and an Approach to Intramolecular Stabilized Silylium Ions

DOI：
10.1002/ejic.201801273
发表时间：
2019-02
期刊：
European Journal of Inorganic Chemistry
影响因子：
2.3
作者：
W. Uhl;Michael Tolzmann;Kira Willeke;Christian Honacker;A. Hepp;M. Layh;E. Würthwein
通讯作者：
W. Uhl;Michael Tolzmann;Kira Willeke;Christian Honacker;A. Hepp;M. Layh;E. Würthwein

Hydrometallation of amino-trialkynylsilanes--intramolecular M-N interactions (M = Al, Ga) and potential activation of Si-N bonds.

氨基三炔基硅烷的加氢金属化——分子内 M-N 相互作用 (M = Al, Ga) 和 Si-N 键的潜在活化