Electrocatalytic Reduction of CO 2 and H 2 O with Zn(II) Complexes Through Metal-Ligand Cooperation.

Authors :: Norouziyanlakvan S
Berro P
Rao GK
Gabidullin B
Richeson D
Source :: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Apr 11; Vol. 30 (21), pp. e202303147. Date of Electronic Publication: 2024 Mar 07.
Publication Year :: 2024
Abstract: Air and water-stable zinc (II) complexes of neutral pincer bis(diphenylphosphino)-2,6-di(amino)pyridine ("PN <superscript>3</superscript> P") ligands are reported. These compounds, [Zn(κ <superscript>2</superscript> -2,6-{Ph <subscript>2</subscript> PNR} <subscript>2</subscript> (NC <subscript>5</subscript> H <subscript>3</subscript> ))Br <subscript>2</subscript> ] (R=Me, 1; R=H, 2), were shown to be capable of electrocatalytic reduction of CO <subscript>2</subscript> at -2.3 V vs. Fc <superscript>+/0</superscript> to selectively yield CO in mixed water/acetonitrile solutions. These complexes also electrocatalytically generate H <subscript>2</subscript> 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 PN <superscript>3</superscript> P ligand. Furthermore, computational analysis suggested a mechanism involving metal-ligand cooperation of a Lewis acidic Zn(II) and a basic ligand.<br /> (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

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