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- Title
Electrocatalytic Reduction of CO<sub>2</sub> and H<sub>2</sub>O with Zn(II) Complexes Through Metal‐Ligand Cooperation.
- Authors
Norouziyanlakvan, Somayeh; Berro, Patrick; Rao, Gyandshwar Kumar; Gabidullin, Bulat; Richeson, Darrin
- Abstract
Air and water‐stable zinc (II) complexes of neutral pincer bis(diphenylphosphino)‐2,6‐di(amino)pyridine ("PN3P") ligands are reported. These compounds, [Zn(κ2‐2,6‐{Ph2PNR}2(NC5H3))Br2] (R=Me, 1; R=H, 2), were shown to be capable of electrocatalytic reduction of CO2 at −2.3 V vs. Fc+/0 to selectively yield CO in mixed water/acetonitrile solutions. These complexes also electrocatalytically generate H2 from water in acetonitrile solutions, at the same potential, with Faradaic efficiencies of up to 90 %. DFT computations support a proposed mechanism involving the first reduction of 1 or 2 occurring at the PN3P ligand. Furthermore, computational analysis suggested a mechanism involving metal‐ligand cooperation of a Lewis acidic Zn(II) and a basic ligand.
- Subjects
ACETONITRILE; COOPERATION; CARBON dioxide; PYRIDINE; LIGANDS (Chemistry)
- Publication
Chemistry - A European Journal, 2024, Vol 30, Issue 21, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202303147