The journal ChemElectroChem features on its front cover the recently published research article “The Dual Effect of Coordinating -NH Groups and Light in the Electrochemical CO2 Reduction with Pyridylamino Co Complexes”, a collaboration between ICIQ and IQCC.
CO2 electroreduction could be improved by applying conceptualized strategies to overcome catalytic bottlenecks. In this regard, we report two new cobalt(II) complexes [Co(Py2RN3)(OTf)](OTf) (CoR, R=H, Me) based on a new C2-symmetric pentacoordinate chiral ligand that are active on the electrochemical CO2 reduction to CO. One of the complexes has a N-H group oriented towards the CO2 binding site (CoH), while the other has a N-Me group with the same orientation (CoMe), as showed by X-ray diffraction. We have studied the effect of introducing hydrogen bonding sites, i.e. N-H in CoH, as a strategy to stabilize reaction intermediates. The complex bearing coordinating unprotected N-H group (CoH) displays catalytic CO2 reduction at the CoII/I redox potential (-1.9 V vs. Fc, ca. 40 % FYCO) whereas CoMe shows CO2 reduction at the CoI/0 redox pair. FTIR-SEC and DFT calculations identified a [CoI?CO]+ cation as catalytic intermediate. The beneficial effect of the N-H group has been attributed to the stabilization of reaction intermediates or transition states and by the larger electron-donating capacity, thus enhancing the nucleophilic character of the CoI intermediate. The study also points to the CO dissociation from the Co(I)-CO resting state intermediate as one of the bottlenecks of the catalytic cycle, which can be overcome with light irradiation, resulting in an increase of the total CO production (-1.9 V, 81 % FYCO, 11.2 TONCO) at the CoII/I redox potential.
The Cover Feature illustrates the proposed mechanism for the electrocatalytic CO2 reduction to CO by the cobalt complex CoH, obtained by the combination of electrochemical, spectroscopic and theoretical studies, highlighting the CO labilization by blue light. Bringing light into the mechanism helped to improve the catalytic performance.
The corresponding paper was recently published in ChemElectroChem:
S. Fernández, S. Cañellas, F. Franco, J.M. Luis, M.À. Pericàs, and J. Lloret?Fillol
“The Dual Effect of Coordinating ?NH Groups and Light in the Electrochemical CO2 Reduction with Pyridylamino Co Complexes” ChemElectroChem2021, ASAP-
Girona, 29 Nov., 2021
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The Institute of Computational Chemistry and Catalysis (IQCC) of the University of Girona (UdG) is a worldwide reference unit in computational chemistry and catalysis that aims at carrying out groundbreaking research on predictive chemistry for catalysis, with special focus on the processes occurring at the confined space for the coming years. [More]