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Keywords:

  • boron;
  • borylene ligands;
  • cations;
  • insertion;
  • iron
Thumbnail image of graphical abstract

One thing leads to another: Reactions of the cationic BN vinylidene analogues 1-[BArF4] (R=Cy, iPr; ArF=3,5-(CF3)2C6H3) towards dicyclohexylcarbodiimide proceed by unprecedented insertion chemistry for terminal borylene complexes. Controlled, stepwise insertion into the Fe[DOUBLE BOND]B and B[DOUBLE BOND]N bonds is demonstrated, sequentially forming four-membered rings linked at a spirocyclic boronium center.