Different ligand platforms, two metals and one goal: CO2RR

Dr. Orestes Rivada-Wheelaghan, Inorganic Chemistry Department, Universidad de Sevilla. Instituto de investigaciones Químicas, CicCartuja, Av. Américo Vespucio 49, 41092, Sevilla, España.

E-mail: orivada@us.esLink opens in a new window

Abstract

Molecular electrocatalysts have received a renewed interest due to their capabilities towards sustainable and energy–efficient redox chemical transformations.¹ Particularly, those involved in new strategies towards energy storage application.^{1a, 2} Hence, I will present our first means of molecular cooperativity under electrochemical reduction conditions targeting carbon dioxide reduction.³

First, I will provide direct experimental evidence on the correlation of remote interactions on MnI- and ReI-complexes with redox potential tuning. Additionally, the electrochemical behavior of the Mn-complex towards carbon dioxide will be discuss, including the effects of added alkali salts using cyclic voltammetry.^3a Later, I will present the formation, characterization and use of a homo-bimetallic complex bearing a pyrazole-based ligand substituted with terpyridine groups at the 3 and 5 positions, for the electrocatalytic reduction carbon dioxide to carbon monoxide in the presence of Brönsted acids.^3b Furthermore, I will present the selective formation of different heterobimetallic complexes bearing “flexible” terpyridine-based ligands, their characterization and preliminary photocatalytic studies towards CO2RR.

Scheme 1. Bimetallic complexes used for CO2RR stabilized with different ligands.

References

(1) a) N. W. Kinzel, C. Werlé, W. Leitner, Angew. Chem. Int. Ed. 2021, 60, 11628–11686; b) N. Wolff, O. Rivada‐Wheelaghan, D. Tocqueville, ChemElectroChem 2021, 8, 4019–4027.

(2) a) T. R. Cook, D. K. Dogutan, S. Y. Reece, Y. Surendranath, T. S. Teets, D. G. Nocera, Chem. Rev. 2010, 110, 6474–6502.

(3) a) A. Srinivasan, J. Campos, N. Giraud, M. Robert, O. Rivada–Wheelaghan, Dalton Trans. 2020, 49, 16623–16626; b) A. Bohn, J. J. Moreno, P. Thuéry, M. Robert, O. Rivada-Wheelaghan, Chem. Eur. J. 2023, e202202361.