Rouen Mathieu, Queval Pierre, Falivene Laura, Allard Jessica, Toupet Loïc, Crévisy Christophe, Caijo Frédéric, Baslé Olivier, Cavallo Luigi, Mauduit Marc
Ecole Nationale Supérieure de Chimie de Rennes, UMR CNRS 6626, 11 Allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7 (France).
Chemistry. 2014 Oct 13;20(42):13716-21. doi: 10.1002/chem.201403934. Epub 2014 Sep 11.
An unexpected cationic bis-N-heterocyclic carbene (NHC) benzylidene ether based ruthenium complex (2 a) was prepared through the double incorporation of an unsymmetrical unsaturated N-heterocyclic carbene (U2 -NHC) ligand that bore an N-substituted cyclododecyl side chain. The isolation and full characterization (including X-ray diffraction studies) of key synthetic intermediates along with theoretical calculations allowed us to understand the mechanism of the overall cationization process. Finally, the newly developed complex 2 a displayed interesting latent behavior during ring-closing metathesis, which could be "switched on" under acidic conditions.
通过双引入带有N-取代环十二烷基侧链的不对称不饱和N-杂环卡宾(U2-NHC)配体,制备了一种意想不到的基于阳离子双-N-杂环卡宾(NHC)亚苄基醚的钌配合物(2a)。关键合成中间体的分离和全面表征(包括X射线衍射研究)以及理论计算使我们能够理解整个阳离子化过程的机制。最后,新开发的配合物2a在闭环复分解反应中表现出有趣的潜在行为,这种行为在酸性条件下可以“开启”。