Synthesis and structural characterization of 20-membered macrocyclic rings bearing trans-chelating bis(N-heterocyclic carbene) ligands and the catalytic activity of their palladium(ii) complexes

Abstract

Macrocycles consisting of a 20-membered ring containing two imidazolium salt functionalities and of the formula [PhCH₂N(CH₂CH₂CH₂)Im(CH₂CH₂CH₂)₂][Br]₂ (Im = imidazole = 3a, benzimidazole = 3b) were synthesized in 70–75% yields. These salts serve as precursors to macrocycles containing two N-heterocyclic carbene (NHC) moieties. Reaction of the macrocyclic salts 3a and 3b with silver oxide afforded macrocyclic-bis(NHC)silver(I) complexes 4a and 4b. Single-crystal X-ray diffraction studies of macrocyclic-bis(NHC)silver(I) complex 4a revealed a tetranuclear silver core with a short Ag–Ag distance (2.9328 Å). Complexes 4a and 4b serve as carbene transfer reagents to Pd. The treatment of macrocyclic-bis(NHC)silver(I) complexes 4a and 4b with one equivalent of PdCl₂(MeCN)₂ in methylene chloride afforded square-planar trans-macrocyclic-bis(NHC)Pd(II)X₂ complexes 5a and 5b. Preliminary screening of these palladium complexes showed they are competent precatalysts for Heck and Suzuki coupling reactions.