权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

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.

该项目基于对 [Cp*E{M(CO)5}2] (Cp* = eta1-C5Me5; E = P, As; M = Cr, W) 类型的桥联戊二烯配合物的一类特殊化合物的反应行为和后续化学的探索。在这些戊二烯配合物中，西格玛结合的 Cp* 取代基的特定性质与桥联戊烯原子的亲电特性相关，从而导致这些配合物的可微分反应性的独特组合，因此可控制。研究的重点一方面是针对五元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，分别产生作为三元环和四元环衍生物的稳定自由基，为此还可能形成具有新型缺电子键合模式的相应二聚体。选定的产品分别以前所未有的阳离子和阴离子衍生物的形式转移。另一方面，要研究的主要反应通道基于这些起始材料的五环原子的亲核攻击。通过对功能性亲核试剂的反应性进行系统研究，在随后的化学反应中具有α-和β-位反应性功能，有针对性地形成新型复合杂环将成为可能，其特征是大量不同的杂原子序列。通过解络反应，首次获得了游离杂环，这种容易获得的杂环使得戊二烯配合物成为独特的起始材料。根据温度和浓度，研究了对多功能底物的反应性的选择性寻址，以实现选择性和可切换的后续反应。通过这种方式获得以杂环作为连接单元的新低聚物和聚合物。此外，还研究了桥联氨基戊二烯和卤代戊二烯配合物的反应行为，并确定了其与 Cp* 取代衍生物的差异。