Selective Cleavage of the Strong or Weak C–C Bonds in Biphenylene Enabled by Rare-Earth Metals

Miaomiao Zhu^#, Zhengqi Chai^#, Ze-Jie Lv^#, Tianyu Li, Wei Liu , Junnian Wei, and Wen-Xiong Zhang* (^#Authors contributed equally)

J. Am. Chem. Soc. 2023, https://doi.org/10.1021/jacs.3c01466.

Selective cleavage of C–C bonds within arene rings is of great interest but remains elusive, especially for the molecules possessing the active and inert C−C bonds. Here, we report that the active and inert C−C bonds of biphenylene could be controllably cleaved by the reaction of biphenylene, potassium graphite and rare-earth complexes with different metal centers. For scandium, the bond activation occurs at the C_aryl–C_aryl single bond, yielding 9-scandafluorene. For the large Lu, the reaction goes through ring contraction of the aromatic ring in biphenylene to provide benzopentalene dianionic lutetium. The origin of the selectivity and the reaction mechanism were illustrated by the isolation of intermediates and DFT calculations.