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
by Thapa, Rajesh; Kilyanek, Stefan M.
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 angstrom). 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)X-2 complexes 5a and 5b. Preliminary screening of these palladium complexes showed they are competent precatalysts for Heck and Suzuki coupling reactions.
- Journal
- Dalton Transactions
- Volume
- 48
- Issue
- 33
- Year
- 2019
- Start Page
- 12577-12590
- URL
- https://dx.doi.org/10.1039/c9dt02147g
- ISBN/ISSN
- 1477-9234; 1477-9226
- DOI
- 10.1039/c9dt02147g