Department of Chemistry & Biochemistry, University of California , Los Angeles, California 90095, United States.
J Am Chem Soc. 2014 Dec 17;136(50):17410-3. doi: 10.1021/ja510761j. Epub 2014 Dec 8.
A new type of C-H bond activation mediated by rare-earth metals under reducing conditions is reported. The synergy between reductants and rare-earth-metal complexes allows the cleavage of unactivated aromatic C-H bonds. The reaction between rare-earth-metal iodides supported by a 1,1'-ferrocenediamide ligand and potassium graphite in benzene leads to the formation of a 1:1 metal molar ratio of the corresponding metal hydride and metal phenyl complex. A proposed mechanism involving an inverse sandwich arene bimetallic intermediate is supported by experimental and computational studies.
报道了一种在还原条件下由稀土金属介导的新型 C-H 键活化。还原剂和稀土金属配合物之间的协同作用允许非活化芳族 C-H 键的断裂。在苯中,由 1,1'-二茂铁二胺配体支撑的稀土金属碘化物与石墨钾反应,生成相应的金属氢化物和金属苯配合物的 1:1 金属摩尔比。实验和计算研究支持涉及反夹心芳烃双金属中间体的提出的机制。