Two-Electron-Induced Reorganization of Cobalt Coordination and Metal-Ligand Cooperative Redox Shifting Co(I) Reactivity toward CO2 Reduction

Abstract

Electrochemical reorganization of complex structures is directly related to catalytic reactivity; thus, the geometric changes of catalysts induced by electron transfer should be considered to scrutinize the reaction mechanism. Herein, we studied electron-induced reorganization patterns of six-coordinate Co complexes with neutral N-donor ligands. Upon two-electron transfer into a Co center enclosed within a bulky π-acceptor ligand, the catalytic site exhibited different reorganization patterns depending on the ligand characteristics. While a bipyridyl ligand released Co-bound solvent (CH₃CN) to open a reaction site, a phenanthroline ligand caused Co-N_arm (side "arm" of NNN-ligand) bond dissociation. The first electron transfer occurred in the Co(II/I) reduction step and the second electron entered the bulky π-acceptor, of which redox steps were assigned from cyclic voltammograms, magnetic moment measurements, and DFT calculations. In comparison, the Co complex of [NNN^NCH₃-Co(CH₃CN)₃](PF₆)₂ ([1-(CH₃CN)₃](PF₆)₂) showed a high H₂ evolution reactivity (HER), whereas a series of Co complexes with bulky π-acceptors such as [NNN^NCH₃-Co(L)(CH₃CN)](PF₆)₂ (L = phen ([2-CH₃CN](PF₆)₂), bpy ([3-CH₃CN](PF₆)₂), [NNN^NCH₃-Co(tpy)](PF₆)₂ ([4](PF₆)₂), and [NNN^CH₂-Co(phen)(CH₃CN)](PF₆)₂ ([5-CH₃CN](PF₆)₂)) suppressed the HER but rather enhanced the CO₂ reduction reaction. The metal-ligand cooperative redox steps enabled the shift of Co(I) reactivity toward CO₂ reduction. Additionally, the amine pendant attached to the NNN^NCH₃-ligand could stabilize the CO₂ reduction intermediate through the hydrogen-bonding interaction with the Co-CO₂H adduct.