Cui Peng, Comanescu Cezar C, Iluc Vlad M
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556, USA.
Chem Commun (Camb). 2015 Apr 11;51(28):6206-9. doi: 10.1039/c5cc00868a.
The reactions of two nucleophilic palladium carbene complexes with the strong Lewis acid B(C6F5)3 afforded two zwitterionic products. One of them features a remote nucleophilic attack at the para-carbon of the supporting ligand, while the other indicates C-F activation of B(C6F5)3. Both behaviours are reminiscent of the reactivity of frustrated Lewis pairs due to the steric inaccessibility of the nucleophilic carbon center, but are unprecedented for transition metal carbene complexes. Furthermore, when those reactions are carried out in the presence of H2, products resulting from H2 splitting are observed.
两种亲核钯卡宾配合物与强路易斯酸B(C6F5)3反应生成了两种两性离子产物。其中一种的特征是在支撑配体的对碳上发生远程亲核进攻,而另一种则表明B(C6F5)3发生了C-F活化。由于亲核碳中心的空间不可及性,这两种行为都让人联想到受阻路易斯对的反应性,但对于过渡金属卡宾配合物来说却是前所未有的。此外,当这些反应在H2存在下进行时,会观察到由H2分裂产生的产物。