Re(I) NHC Complexes for Electrocatalytic Conversion of CO2.

Academic Article


  • The modular construction of ligands around an N-heterocyclic carbene building block represents a flexible synthetic strategy for tuning the electronic properties of metal complexes. Herein, methylbenzimidazolium-pyridine and methylbenzimidazolium-pyrimidine proligands are constructed in high yield using recently established transition-metal-free techniques. Subsequent chelation to ReCl(CO)5 furnishes ReCl(N-methyl-N'-2-pyridylbenzimidazol-2-ylidine)(CO)3 and ReCl(N-methyl-N'-2-pyrimidylbenzimidazol-2-ylidine)(CO)3. These Re(I) NHC complexes are shown to be capable of mediating the two-electron conversion of CO2 following one-electron reduction; the Faradaic efficiency for CO formation is observed to be >60% with minor H2 and HCO2H production. Data from cyclic voltammetry is presented and compared to well-studied ReCl(2,2'-bipyridine)(CO)3 and MnBr(2,2'-bipyridine)(CO)3 systems. Results from density functional theory computations, infrared spectroelectrochemistry, and chemical reductions are also discussed.
  • Authors

  • Stanton, Charles J
  • Machan, Charles W
  • Vandezande, Jonathon E
  • Jin, Tong
  • Majetich, George F
  • Schaefer, Henry F
  • Kubiak, Clifford P
  • Li, Gonghu
  • Agarwal, Jay
  • Status

    Publication Date

  • March 21, 2016
  • Digital Object Identifier (doi)

    Pubmed Id

  • 26950549
  • Start Page

  • 3136
  • End Page

  • 3144
  • Volume

  • 55
  • Issue

  • 6