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Functional Pentelidene Complexes of the heavier Group 15 Elements

较重 15 族元素的功能性戊烯配合物

基本信息

批准号：
141109038
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：
2009
资助国家：
德国
起止时间：
2008-12-31 至 2016-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/141109038?language=en
关键词：
Functional Pentelidene Complexes heavier Group

项目摘要

The project bases on the exploration of the reaction behavior and subsequent chemistry of a special class of compounds of bridged pentelidene complexes of the type [Cp*E{M(CO)5}2] (Cp* = eta1-C5Me5; E = P, As; M = Cr, W). In these pentelidene complexes the specific properties of the sigma-bound Cp*-substituent are linked with the electrophilic character of the bridged pentel atoms, leading to a unique combination of differentiable and therefore controllable reactivity of these complexes. The focus of the investigations is on the one hand directed to the selective photolytic generation of pentel atom radicals and their selective subsequent reactions with different compounds to yield stable radicals as three- and four-membered ring derivatives, respectively, for which also corresponding dimers with novel electron deficient bonding pattern are possible to be formed. Selected products are transferred in unprecedented cationic and anionic derivatives, respectively. On the other hand the main reactions channel to be investigated bases on the nucleophilic attack at the pentel atom of these starting materials. By systematic investigations of the reactivity towards functional nucleophiles, possessing in alpha- and beta-position reactive functions for a subsequent chemistry, the targeted formation of novel complexed heterocycles will be possible, which features a large number of different heteroatom sequences. By decomplexation reactions, for the first time, free heterocycles are obtained, which easy accessibility makes the pentelidene complexes to unique starting materials. In dependency on temperature and concentration a selective addressing of the reactivity towards multifunctional substrates is studied to achieve selective and switchable subsequent reactions. By this way new oligomers and polymers are obtained featuring heterocycles as linking units. Moreover, the reaction behavior of bridged aminopentelidene and halogenopentelidene complexes is studied and the differences to Cp* substituted derivatives are determined.

该项目的基础上探索的反应行为和随后的化学的一类特殊的化合物的桥接pentelidene配合物的类型[Cp*E{M（CO）5}2]（Cp* = eta 1-C5 Me 5; E = P，As; M = Cr，W）。在这些pentelidene配合物的σ-键合Cp*-取代基的特定性能与桥接pentel原子的亲电特性相关联，导致这些配合物的独特组合的可区分的，因此可控的反应性。调查的重点是一方面针对pentel原子自由基的选择性光解生成及其与不同化合物的选择性后续反应，以分别产生稳定的自由基作为三元环和四元环衍生物，其中也有可能形成相应的二聚体与新的缺电子键合模式。所选产品分别以前所未有的阳离子和阴离子衍生物形式转移。另一方面，研究的主要反应通道是基于这些起始原料的五原子上的亲核进攻。通过对功能性亲核试剂的反应性的系统研究，在α-和β-位具有用于后续化学的反应性官能团，靶向形成新的复合杂环将是可能的，其特征在于大量不同的杂原子序列。通过解络合反应，第一次获得了游离杂环，其容易获得性使得五亚甲基络合物成为独特的起始材料。在依赖于温度和浓度的多功能底物的反应性的选择性寻址进行了研究，以实现选择性和可切换的后续反应。通过这种方式，获得了以杂环为连接单元的新的低聚物和聚合物。此外，研究了桥连氨基亚戊烯和卤代亚戊烯配合物的反应行为，并确定了与Cp* 取代衍生物的差异。