The synthesis of new PEPPSI-type N-heterocyclic carbene (NHC)-Pd(II) complexes bearing long alkyl chain as precursors for the synthesis of NHC-stabilized Pd(0) nanoparticles and their catalytic applications

Abstract

Six new N-heterocyclic carbene (NHC) ligands bearing long-chain alkyl groups on N-atom of 5,6-dimethylbenzimidazole skeleton and their Pd(II) complexes (PEPPSI type) with a close formula of trans-[PdX2(NHC)Py] (X = Cl or Br; Py = pyridine) were successfully synthesized. The yielded NHC ligands and their Pd(II) complexes were characterized by elemental analysis, 1H- and 13C NMR, FT-IR spectroscopy, and mass spectroscopy and the molecular structure of 3f was determined by X-ray crystallography. All synthesized NHC-Pd(II) complexes were air-stable both as powder and in solution under ambient conditions, which allow us to test them as catalysts in Suzuki-Miyaura cross-coupling (SMC) reactions and to use them as precursors for the in situ synthesis of NHC-stabilized Pd(0) nanoparticles (NPs) during the dehydrogenation of ammonia borane (AB) in dry tetrahydrofuran solution at room temperature. In this protocol, AB served both as a reducing agent for the reduction of NHC-Pd(II) complexes to yield NHC-stabilized Pd(0) NPs and a chemical hydrogen storage material for the concomitant hydrogen generation. The in situ synthesized NHC-stabilized Pd(0) NPs were characterized by UV–Vis spectroscopy, TEM, and XRD techniques. The catalytic activity of the in situ generated NHC-stabilized Pd(0) NPs in the dehydrogenation of AB was followed by measuring the volume of hydrogen generated versus time at room temperature. Among the five different NHC-Pd(II) complexes, 3c (dichloro[1-octadesyl-3-(2,4,6-trimethylbenzyl)-(5,6-dimethylbenzimidazol-2-ylidene)](pyridine)palladium(II)) yielded the most stable Pd(0) NPs along with the highest catalytic activity in the dehydrogenation of AB (TOF= 37.7 min−1 at 1 eqv. H2 release). The 11B-NMR analysis of the THF solution after the catalytic dehydrogenation of AB revealed the formation of cyclopolyborazane, which is one of the important dehydrocoupling products of AB. Additionally, all NHC-Pd(II) complexes provided high yields in the SMC reactions of phenylboronic acid with various aryl bromides bearing electron-withdrawing or electron-donating groups and even for aryl chlorides bearing electron-withdrawing group at room temperature with the low catalyst loadings. This study revealed that the length of the alkyl chain of NHC ligands has a significant effect on the catalytic activity of the NHC-Pd(II) complexes in the SMC reactions, the longer the alkyl chain on the N atom of NHC ligand, the higher activity of NHC-Pd(II) complex in SMC reactions. It also influences the particle size, morphology and catalytic activity of in situ generated Pd(0) NPs in the dehydrogenation of AB.