Air-stable, convenient to handle Pd based PEPPSI (pyridine enhanced precatalyst preparation, stabilization and initiation) themed precatalysts of N/O-functionalized N-heterocyclic carbenes and its utility in Suzuki-Miyaura cross-coupling reaction.
Several new air-stable, convenient to handle and easily synthesized Pd based PEPPSI (Pyridine Enhanced Precatalyst Preparation, Stabilization and Initiation) type precatalysts supported over N/O-functionalized N-heterocyclic carbenes (NHC) namely, trans-[1-(benzyl)-3-(N-t-butylacetamido)imidazol-2-ylidene]Pd(pyridine)Cl2 (), trans-[1-(2-hydroxy-cyclohexyl)-3-(benzyl)imidazol-2-ylidene]Pd(pyridine)Cl2 () and trans-[1-(o-methoxybenzyl)-3-(t-butyl)imidazol-2-ylidene]Pd(pyridine)Br2 (), have been designed. Specifically, the Pd-NHC complexes, , and , were conveniently synthesized from their respective imidazolium halide salts by the reaction with PdCl2 in pyridine in presence of K2CO3 as a base. A new imidazolium chloride salt, 1-(benzyl)-3-(N-t-butylacetamido)imidazolium chloride () was synthesized by the alkylation reaction of benzyl imidazole with N-t-butyl-2-chloroacetamide. The molecular structures of the imidazolium chloride salt, , and the Pd-NHC complexes, , and , have been determined by X-ray diffraction studies. The density functional theory studies of the , and complexes were carried out to in order to gain insight about their structure, bonding and the electronic properties. The nature of the NHC-metal bond in these complexes was examined using Charge Decomposition Analysis (CDA), which revealed that the N-heterocyclic carbene ligands are effective sigma-donors. In addition, the catalysis studies revealed that the Pd-NHC complexes, , and , are effective catalysts for the Suzuki-Miyaura type C-C cross-coupling reactions.
Ray
Lipika
L
Department of Chemistry, Powai, Mumbai, 400 076.
Shaikh
Mobin M
MM
Ghosh
Prasenjit
P