A series of bis-NHC pincer complexes of palladium(II) have been prepared and characterized. These pyridyl-spaced dicarbene complexes ([(PDCR)Pd(MeCN)](PF6)2) were synthesized with substituents of varying steric bulk at the wingtip positions, which include R = methyl, ethyl, isopropyl, cyclohexyl, mesityl and 2,6-diisopropylphenyl. The synthesis of this library of complexes was accomplished either by direct metallation of the prerequisite pyridyl-spaced bis-imidazolium proligands with Pd(OAc)2 or via treatment with Ag2O to afford the corresponding silver carbenes, which were then transmetallated onto palladium. Solid-state structures for each of the [(PDCR)Pd(MeCN)](PF6)2 derivatives were obtained via X-ray crystallography and allowed for the steric properties of each PDCR ligand to be evaluated by two methods. These analyses, which included calculation of the percent buried volume (%VBur) and solid angles of the PDCR ligands, served to characterize the steric environment around the palladium center in each of the complexes that was prepared. Finally, voltammetry and controlled potential electrolysis studies were performed to characterize the redox chemistry of the [(PDCR)Pd(MeCN)](PF6)2 derivatives and assess if they could electrocatalyze the reduction of CO2. The influence of the steric properties of the PDCR ligand on the electrochemistry of the resulting complexes [(PDCR)Pd(MeCN)](PF6)2 is also discussed.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.