Skeletal Rearrangement Process in Organometallic Cations of Group 14 Elements - A Powerful Concept for Assembling Complex Polysilane Frameworks

第 14 族元素有机金属阳离子的骨架重排过程 - 组装复杂聚硅烷框架的强大概念

基本信息

批准号：
193247165
负责人：
Professor Dr. Thomas Müller
金额：
--
依托单位：
Institut für Chemie (IfC)
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2011
资助国家：
德国
起止时间：
2010-12-31 至 2014-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/193247165?language=en
关键词：
Skeletal Rearrangement Process Organometallic Cations

项目摘要

Despite the highly interesting electronic properties and the technological potential of polysilanes the chemist’s repertoire for their synthesis or structural manipulation is mostly limited to the Wurtz type coupling reaction. In this connection Lewis acid catalyzed rearrangement reactions represent an interesting method to access molecular structures, which are otherwise difficult to obtain. Closely related to the well know Wagner-Meerwein rearrangement, it is a much more facile process for polysilanes. Although first examples of polysilane rearrangement have been reported almost 40 years ago not much is known about the governing principles of this reaction. The current project, to be carried out by the groups in Oldenburg and Graz, proposes a joint study comprising new synthetic approaches, investigations of intermediates and reaction mechanisms, both supported by computational methods. Preliminary studies have already shown that the reaction of isomeric polysilanes with aluminum chloride can result in the formation of rather complex structures such as an adamantane type tricyclic polysilane. In addition it was found that germanium containing polysilanes rearrange with the germanium atoms selectively moved to trisilylated positions of the product.Other preliminary results suggest the Lewis acid catalyzed reaction can also be used for the synthesis of polysilanes containing alkylene units and even further for the preparation of complex carbosilanes. The synthetic work in this project, conducted by the Austrian group, will benefit from the theoretical and basic studies (of the German group) which will provide insight into the underlying principles of the chemistry. On the other hand will the synthetic work allow formulating new questions which will be addressed by computational methods. The unique combined synthetic and theoretical expertise of the two groups will allow the best possible treatment of the complex matter of Lewis acid catalyzed rearrangement reactions.

尽管具有非常有趣的电子特性以及多硅烷的技术潜力，但化学家的合成或结构操作的曲目主要限于Wurtz型耦合反应。在这方面，路易斯酸催化的重排反应代表了访问分子结构的有趣方法，否则难以获得。与知名的Wagner-Meerwein重排密切相关，这对于多乙烷来说是一个更加便利的过程。尽管大约40年前据报道多硅烷重排的第一个例子对此反应的管理原理并不了解。当前的项目将由奥尔登堡和格拉兹的小组进行，提议一项联合研究完成了新的合成方法，对中间体的研究和反应机制，均由计算方法支持。初步研究已经表明，异构体多硅烷与氯化铝的反应会导致形成相当复杂的结构，例如阿甘坦型三环类多硅烷。此外，发现含有多去葡萄干的锗与锗原子有选择地移动到产品的三甲硅烷基原子。其他的结果表明，刘易斯酸催化的反应也可用于合成含烷基烯单位的多硅烷，甚至可以进一步制备复合型碳硅烷的准备。奥地利集团进行的该项目中的合成工作将受益于理论和基础研究（德国集团），该研究将提供对化学基本原理的见识。另一方面，合成工作将允许提出新问题，这些问题将通过计算方法解决。两组的独特合成和理论专业知识将允许对刘易斯酸催化重排反应的复杂物质的最佳处理。