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 H-2 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.