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Reduction-induced CO dissociation by a [Mn(bpy)(CO)4][SbF6] complex and its relevance in electrocatalytic CO2 reduction

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Abstract

[Mn(bpy)(CO)3Br] is recognized as a benchmark electrocatalyst for CO2 reduction to CO, with the doubly reduced [Mn(bpy)(CO)3] proposed to be the active species in the catalytic mechanism. The reaction of this intermediate with CO2 and two protons is expected to produce the tetracarbonyl cation, [Mn(bpy)(CO)4]+, thereby closing the catalytic cycle. However, this species has not been experimentally observed. In this study, [Mn(bpy)(CO)4][SbF6] (1) was directly synthesized and found to be an efficient electrocatalyst for the reduction of CO2 to CO in the presence of H2O. Complex 1 was characterized using X-ray crystallography as well as IR and UV-Vis spectroscopy. The redox activity of 1 was determined using cyclic voltammetry and compared with that of benchmark manganese complexes, e.g., [Mn(bpy)(CO)3Br] (2) and [Mn(bpy)(CO)3(MeCN)][PF6] (3). Infrared spectroscopic analyses indicated that CO dissociation occurs after a single-electron reduction of complex 1, producing a [Mn(bpy)(CO)3(MeCN)]+ species. Complex 1 was experimentally verified as both a precatalyst and an on-cycle intermediate in homogeneous Mn-based electrocatalytic CO2 reduction.

Graphical abstract: Reduction-induced CO dissociation by a [Mn(bpy)(CO)4][SbF6] complex and its relevance in electrocatalytic CO2 reduction

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Supplementary files

Article information


Submitted
24 Oct 2019
Accepted
11 Dec 2019
First published
12 Dec 2019

Dalton Trans., 2020, Advance Article
Article type
Paper

Reduction-induced CO dissociation by a [Mn(bpy)(CO)4][SbF6] complex and its relevance in electrocatalytic CO2 reduction

H. Kuo, S. E. Tignor, T. S. Lee, D. Ni, J. E. Park, G. D. Scholes and A. B. Bocarsly, Dalton Trans., 2020, Advance Article , DOI: 10.1039/C9DT04150H

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