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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.

尽管聚硅烷具有非常有趣的电子性质和技术潜力，但化学家对其合成或结构操纵的所有方法大多限于Wurtz型偶联反应。在这方面，刘易斯酸催化的重排反应代表了一种获得分子结构的有趣方法，否则很难获得分子结构。与众所周知的Wagner-Meerwein重排密切相关，它是一种更容易制备聚硅烷的方法。虽然聚硅烷重排的第一个例子在大约40年前就已经报道了，但人们对这种反应的控制原理知之甚少。目前的项目将由奥尔登堡和格拉兹的研究小组进行，提出了一项联合研究，包括新的合成方法，中间体和反应机制的研究，两者都得到了计算方法的支持。初步研究已经表明，异构聚硅烷与氯化铝的反应可以导致形成相当复杂的结构，例如金刚烷型三环聚硅烷。此外，还发现含锗聚硅烷发生重排，锗原子选择性地移动到产物的三甲硅烷基化位置，其它初步结果表明，刘易斯酸催化的反应也可用于合成含亚烷基单元的聚硅烷，甚至进一步用于制备复合碳硅烷。由奥地利小组进行的这一项目的综合工作将受益于（德国小组的）理论和基础研究，这些研究将深入了解化学的基本原理。另一方面，综合工作将允许制定新的问题，将通过计算方法来解决。这两个小组的独特的合成和理论专长将使刘易斯酸催化重排反应的复杂物质的最佳可能的治疗。