Dinuclear Rhenium Complex with a Proton Responsive Ligand as a Redox Catalyst for the Electrochemical CO2 Reduction
2017 | journal article; research paper. A publication with affiliation to the University of Göttingen.
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- Authors
- Wilting, Alexander ; Stolper, Thorsten; Mata, Ricardo A. ; Siewert, Inke
- Abstract
- Herein, we present the reduction chemistry of a [GRAPHIC] dinuclear alpha-diimine rhenium complex, 1, [Re-2(L)(CO)(6)Cl-2], with a proton responsive ligand and its application as a catalyst in the electrochemical CO2, reduction reaction (L = 4-tert-butyl-2,6-bis(6-(1H-imidazol-2-y1)-pyridin-2-yl)phenol). The complex has a phenol group in close proximity to the active center, which may act as a proton relay during catalysis, and pyridine-NH-imidazole units as alpha-diimine donors. The complex is an active catalyst for the electrochemical CO, reduction reaction. CO is the main product after catalysis, and only small amounts of H-2 were observed, which can be related to the ligand reactivity. The i(c)/i(p) ratio of 20 in dimethylformamide (DMF) + 10% water for 1 points to a higher activity with regard to [Re(bpy)(CO)(3)Cl] in MeCN/H2O, albeit 1 requires a slightly larger overpotential (bpy = 2,2-bipyridine). Spectroscopic and theoretical investigations revealed detailed information about the reduction chemistry of 1. The complex exhibits two reduction processes in DMF, and each process was identified as a two-electron reduction in the absence of CO, The first 2e(-) reduction is ligand based and leads to homolytic N-H bond cleavage reactions at the imidazole units of 1, which is equal to a net double proton removal from 1 forming [Re2(LH-2)(CO)(6)Cl-2](2-). The second 2e(-) reduction process has been identified as an O-H bond cleavage reaction at the phenol group, removal of chloride ions from the coordination spheres of the metal ions, and a ligand-centered one-electron reduction of [Re-2(LH-3)(CO)(6)Cl](2-). In the presence of CO2, the second reduction process initiates catalysis. The reduced species is highly nucleophilic and likely favors the reaction with CO, instead of O-H bond cleavage.
- Issue Date
- 2017
- Journal
- Inorganic Chemistry
- Project
- SFB 1073: Kontrolle von Energiewandlung auf atomaren Skalen
SFB 1073 | Topical Area C | C01 Hydrid-Anordnungen für die Untersuchung photo-induzierter mehrstufiger katalytischer Prozesse
SFB 1073 | Topical Area C | C03 Vom Elektronentransfer zur chemischen Energiespeicherung: ab-initio Untersuchungen korrelierter Prozesse - ISSN
- 0020-1669
- eISSN
- 1520-510X
- Language
- English