Jump to main content
Jump to site search

Issue 5, 2019
Previous Article Next Article

Ligand-centered electrochemical processes enable CO2 reduction with a nickel bis(triazapentadienyl) complex

Author affiliations

Abstract

We report the synthesis of Ni(TAPPy)2 (TAPPy = 1,3,5-triazapentadienyl-2,4-bis(2-pyridyl)) and its reactivity with CO2 under reducing conditions. Electrochemical reduction of Ni(TAPPy)2 under inert gas reveals that the complex accommodates up to two additional electrons, with DFT calculations indicating that electron density is delocalized almost exclusively onto the TAPPy ligand framework. The singly reduced product [K(crypt)][Ni(TAPPy)2] (crypt = 2.2.2-cryptand) has been synthesized, and its EPR data is consistent with having ligand-based radical anion character. Controlled potential electrolysis experiments reveal that reduced Ni(TAPPy)2 converts CO2 to form CO; however, spectroscopic and computational data indicate that deactivation readily occurs to form Ni(L)(CO)n compounds, CO32−, and carboxylated (RCOO) ligand decomposition products. This study highlights that redox activity at the ligand can play an important role during the reduction of CO2 using transition metal complexes.

Graphical abstract: Ligand-centered electrochemical processes enable CO2 reduction with a nickel bis(triazapentadienyl) complex

Back to tab navigation

Supplementary files

Article information


Submitted
19 Dec 2018
Accepted
21 Mar 2019
First published
21 Mar 2019

Sustainable Energy Fuels, 2019,3, 1172-1181
Article type
Paper

Ligand-centered electrochemical processes enable CO2 reduction with a nickel bis(triazapentadienyl) complex

Z. Dubrawski, J. Heidebrecht, B. M. Puerta Lombardi, A. S. Hyla, J. Willkomm, C. L. Radford, J. Lin, G. C. Welch, S. Ponnurangam, R. Roesler, D. E. Prokopchuk and W. E. Piers, Sustainable Energy Fuels, 2019, 3, 1172
DOI: 10.1039/C8SE00623G

Social activity

Search articles by author

Spotlight

Advertisements