Enhanced π-back-donation resulting in the trans labilization of a pyridine ligand in an N-heterocyclic carbene (NHC) PdII precatalyst: a case study

Abstract

The molecular structure of the benzimidazol-2-ylidene-PdCl2-pyridine-type PEPPSI (pyridine-enhanced precatalyst, preparation, stabilization and initiation) complex {1,3-bis[2-(diisopropylamino) ethyl] benzimidazol-2-ylidene-kappa C-2}dichlorido(pyridine-kappa N) palladium(II), [PdCl2(C5H5N)(C23H40N4)], has been characterized by elemental analysis, IR and NMR spectroscopy, and natural bond orbital (NBO) and charge decomposition analysis (CDA). Cambridge Structural Database (CSD) searches were used to understand the structural characteristics of the PEPPSI complexes in comparison with the usual Nheterocyclic carbene (NHC) complexes. The presence of weak C-H center dot center dot center dot Cl-type hydrogen-bond and pi-pi stacking interactions between benzene rings were verified using NCI plots and Hirshfeld surface analysis. The preferred method in the CDA of PEPPSI complexes is to separate their geometries into only two fragments, i. e. the bulky NHC ligand and the remaining fragment. In this study, the geometry of the PEPPSI complex is separated into five fragments, namely benzimidazol-2-ylidene (Bimy), two chlorides, pyridine (Py) and the Pd II ion. Thus, the individual roles of the Pd atom and the Py ligand in the donation and back-donation mechanisms have been clearly revealed. The NHC ligand in the PEPPSI complex in this study acts as a strong pi-donor with a considerable amount of pi-back-donation from Pd to Ccarbene. The electron-poor character of Pd II is supported by pi-back-donation from the Pd centre and the weakness of the Pd-N(Py) bond. According to CSD searches, Bimy ligands in PEPPSI complexes have a stronger pi-donating ability than imidazol-2-ylidene ligands in PEPPSI complexes.