Structure and Bonding in Neutral and Cationic 14-Electron Gold Alkyne π Complexes
Structure and Bonding in Neutral and Cationic 14-Electron Gold Alkyne π Complexes
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DOI：
10.1002/chem.200901062
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发表时间：
2009-01-01
影响因子：
4.3
通讯作者：
Fuerstner, Alois
中科院分区：
文献类型：
--
作者：
Fluegge, Susanne;Anoop, Anakuthil;Fuerstner, Alois
以环十二炔(5)为原型，将其与中性的[AuCl]片段或两种不同的阳离子[Au(NHC)](+)实体(NHC=N-杂环卡宾)配位，得到了化合物6、8和10，并用X-射线单晶和核磁共振进行了表征。由于在原位晶化后也可以得到固态环十二炔的结构，因此可以进行比较，以深入了解不同的金碎片对炔烃结构的影响。这些数据是根据对单个化合物中的成键情况的DFT分析来解释的，该分析提供了对许多金催化转化共同的第一个基本步骤的见解。
Cyclododecyne (5) as a prototype unstrained alkyne was coordinated to either the neutral [AuCl] fragment or to two different cationic [Au(NHC)](+) entities (NHC=N-heterocyclic carbene), and the resulting complexes 6, 8, and 10 were characterized by X-ray crystallography and NMR spectroscopy. Since the structure of cyclododecyne in the solid state could also be obtained after in situ crystallization, a comparison was possible that provides insights into structural changes imposed on the alkyne by the different gold fragments. These data are interpreted on the basis of a DFT analysis of the bonding situation in the individual compounds, which provides insights into the very first elementary step common to many gold-catalyzed transformations.