Electrochemical Reduction of CO2 Catalyzed by Re(pyridine-oxazoline)(CO)3Cl Complexes

John K. Nganga, Christian R. Samanamu, Joseph M. Tanski, Carlos Pacheco, Cesar Saucedo, Victor S. Batista, Kyle A. Grice, Mehmed Z. Ertem, Alfredo M. Angeles-Boza

Research output: Contribution to journalArticlepeer-review

25 Scopus citations

Abstract

A series of rhenium tricarbonyl complexes coordinated by asymmetric diimine ligands containing a pyridine moiety bound to an oxazoline ring were synthesized, structurally and electrochemically characterized, and screened for CO2 reduction ability. The reported complexes are of the type Re(N-N)(CO)3Cl, with N-N = 2-(pyridin-2-yl)-4,5-dihydrooxazole (1), 5-methyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (2), and 5-phenyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (3). The electrocatalytic reduction of CO2 by these complexes was observed in a variety of solvents and proceeds more quickly in acetonitrile than in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The analysis of the catalytic cycle for electrochemical CO2 reduction by 1 in acetonitrile using density functional theory (DFT) supports the C-O bond cleavage step being the rate-determining step (RDS) (ΔG = 27.2 kcal mol-1). The dependency of the turnover frequencies (TOFs) on the donor number (DN) of the solvent also supports that C-O bond cleavage is the rate-determining step. Moreover, the calculations using explicit solvent molecules indicate that the solvent dependence likely arises from a protonation-first mechanism. Unlike other complexes derived from fac-Re(bpy)(CO)3Cl (I; bpy = 2,2′-bipyridine), in which one of the pyridyl moieties in the bpy ligand is replaced by another imine, no catalytic enhancement occurs during the first reduction potential. Remarkably, catalysts 1 and 2 display relative turnover frequencies, (icat/ip)2, up to 7 times larger than that of I.

Original languageEnglish (US)
Pages (from-to)3214-3226
Number of pages13
JournalInorganic chemistry
Volume56
Issue number6
DOIs
StatePublished - Mar 20 2017

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Electrochemical Reduction of CO<sub>2</sub> Catalyzed by Re(pyridine-oxazoline)(CO)<sub>3</sub>Cl Complexes'. Together they form a unique fingerprint.

Cite this