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, H-1- and C-13 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-octadesyl3-(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. H-2 release). The B-11-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. (C) 2020 Elsevier B.V. All rights reserved.