Exploration of Pynaphthyridine and Binaphthyridine Manganese(I) Tricarbonyl Complexes: Influence on Carbon Dioxide Reduction Electrocatalysis

• Published in: Organometallics Vol. 43; no. 14; pp. 1517 - 1527
• Main Authors: Cohen, Kailyn Y., Simonyan, Hovnan, Ortiz, Mason, Solomon, Benjamin F., Simkins, Luke, Dominey, Raymond N., Goldman, Emma W., Bocarsly, Andrew B.
• Format: Journal Article
• Language: English
• Published: American Chemical Society 22.07.2024
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/acs.organomet.4c00008

For CO2 electrocatalysts of the form fac-[Mn­(diimine)­(CO)3Br], we previously reported that expanding the π-system of the chelating ligand from 2,2′-bipyridine (bpy) to 2-(2-pyridyl)­quinoline (pq) to 2,2′-biquinoline (bqn) introduced a shift in the mechanism for CO2 reduction to CO. Here, we have synthesized pynaphthyridine and binaphthyridine ligands which incorporate extra nitrogen atoms that can act as H-bond acceptors. Though these ligands redshift the MLCT bands, which has previously been associated with a decrease in electrocatalytic performance for CO2 reduction, MnBr­(1,8-pynap) in acetonitrile (MeCN) displays a smaller overpotential for CO2 reduction than MnBr­(pq). This effect was not observed in N,N-dimethylformamide (DMF), suggesting that H-bonding plays a major role in increasing the catalytic activity. While MnBr­(1,8-bn) also had a higher Faradaic efficiency for CO formation than MnBr­(bqn), it was not more effective than MnBr­(1,8-pynap) in DMF. To demonstrate the importance of the nitrogen ring positions, MnBr­(1,6-pynap) was also synthesized, where the aryl nitrogen is facing away from the Mn center. The MnBr­(1,6-pynap) was a poor electrocatalyst for CO2 reduction, suggesting that the nonligated N atom in the 1,8-complexes stabilizes the Mn–C­(O)­OH intermediate.