Smits G, Audic B, Wodrich M D, Corminboeuf C, Cramer N
Laboratory of Asymmetric Catalysis and Synthesis , EPFL SB ISIC LCSA , BCH 4305 , CH-1015 Lausanne , Switzerland . Email:
Laboratory for Computational Molecular Design , EPFL SB ISIC LCMD , BCH 5312 , CH-1015 Lausanne , Switzerland . Email:
Chem Sci. 2017 Oct 1;8(10):7174-7179. doi: 10.1039/c7sc02986a. Epub 2017 Aug 24.
The electronic and steric properties of tailored cyclopentadienyl (Cp) ligands are powerful handles to modulate the catalytic properties of their metal complexes. This requires the individual preparation, purification and storage of each ligand/metal combination. Alternative, ideally , complexation protocols would be of high utility. We disclose a new approach to access Cp metal complexes. Common metal precursors rapidly react with cyclopentadienyl carbinols β-carbon eliminations to directly give the Cp-metal complexes. An advantage of this is the direct and flexible use of storable pre-ligands. No auxiliary base is required and the Cp complexes can be prepared in the reaction vessel for subsequent catalytic transformations.
定制的环戊二烯基（Cp）配体的电子和空间性质是调节其金属配合物催化性质的有力手段。这需要对每种配体/金属组合进行单独制备、纯化和储存。理想情况下，替代的络合方案将具有很高的实用性。我们公开了一种获得Cp金属配合物的新方法。常见的金属前体与环戊二烯基甲醇迅速反应，通过β-碳消除直接生成Cp-金属配合物。这样做的一个优点是可以直接灵活地使用可储存的前配体。无需辅助碱，并且可以在反应容器中制备Cp配合物以用于后续的催化转化。
