Copper(II) mediated phenol ring nitration by nitrogen dioxide

Abstract

Cu(ii) complexes of N2O2 type ligands, L1H2 and L2H2 [L1H2 = 6,6′-(((pyridin-2-ylmethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol); L2H2 = 2,4-di-tert-butyl-6-(((3-(tert-butyl)-2-hydroxy-5-methylbenzyl)(pyridin-2-yl-methyl)amino)methyl)phenol], have been synthesized. Addition of nitrogen dioxide (NO2) in THF solutions of the complexes resulted in the nitration at the 4-position of a coordinated equatorial phenolate ring of the ligand frameworks. This nitration did not occur at the phenol ring which is axially coordinated to the metal center. Spectroscopic evidence suggests that the reaction proceeds through a phenoxyl radical complex formation. © 2015 The Royal Society of Chemistry.