Easy Synthesis of a Self‐Assembled Imine‐Based Iron(II) Complex Endowed with Crown‐Ether Receptors

Herein we report that an imine‐based iron complex decorated with crown‐ether moieties self‐assembles in CH 3 CN solution from three building blocks (namely Fe(CH 3 CN) 2 (OTf) 2 , 2‐picolylamine and aldehyde 6a ) added in the proper molar ratio (1:2:2, respectively). Aldehyde 6a , endowed with a benzocrown‐ether receptor, can be prepared in two steps from commercial materials with high yields (79 %) and no need of chromatographic separations. The self‐assembled complex is highly stable in CH 3 CN solution. The complex has been tested as catalyst for the oxidation of aromatic compounds endowed with primary ammonium anchoring group with H 2 O 2 . An unexpected yet moderate selectivity for remote meta over ortho hydroxylation was obtained, which is mainly due to the steric hindrance of the catalyst.