title: The Influence of para Substituents in Bis(N-Heterocyclic Carbene) Palladium Pincer Complexes for Electrocatalytic CO2Reduction.
abstract: The effect of modifying the pyridyl para position of lutidine-linked bis(N-heterocyclic carbene) Pd pincer complexes is studied both experimentally (R = OMe, H, Br, and COOR) and computationally, showing a strong effect on the first reduction potential of the complex and allowing the reduction potential to be tuned over a wide range in relation to the Hammett σpconstant of the para substituent. The effect of the pyridyl para substituent on electron density of the metal center, frontier orbital energies, and dissociation energy of the trans ligand are also investigated in the context of reactivity with CO2through electrochemical characterization of the complexes under N2and CO2and controlled potential electrolysis experiments where CO2is reduced to CO.
authors.affiliation: Department of Chemistry, University of British Columbia , 2036 Main Mall, Vancouver, British Columbia V6T 1Z1, Canada.
authors.forename: Jeffrey A
authors.initials: JA
authors.lastname: Therrien
authors.affiliation: Department of Chemistry, University of British Columbia , 2036 Main Mall, Vancouver, British Columbia V6T 1Z1, Canada.
authors.forename: Michael O
authors.identifier: http://orcid.org/0000-0003-3076-790X
authors.initials: MO
authors.lastname: Wolf