A 4H⁺/4e^- Electron-Coupled-Proton Buffer Based on a Mononuclear Cu Complex

In this research article, we describe a 4H⁺/4e^- electron-coupled-proton buffer (ECPB) based on Cu and a redox-active ligand. The protonated/reduced ECPB (complex 1: [Cu(8H), consisting of Cu^I with 2 equiv of the ligand (^catLH₄: 1,1'-(4,5-dimethoxy-1,2-phenylene)bis(3-(tert-butyl)urea)), reacted with H⁺/e^- acceptors such as O₂ to generate the deprotonated/oxidized ECPB. The resulting compound, (complex 5: [Cu(4H), was characterized by X-ray diffraction analysis, nuclear magnetic resonance (¹H-NMR), and density functional theory, and it is electronically described as a cuprous bis(benzoquinonediimine) species. The stoichiometric 4H⁺/4e^- reduction of 5 was carried out with H⁺/e^- donors to generate 1 (Cu^I and 2 equiv of ^catLH₄) and the corresponding oxidation products. The 1/5 ECPB system catalyzed the 4H⁺/4e^- reduction of O₂ to H₂O and the dehydrogenation of organic substrates in a decoupled (oxidations and reductions are separated in time and space) and a coupled fashion (oxidations and reductions coincide in time and space). Mechanistic analysis revealed that upon reductive protonation of 5 and oxidative deprotonation of 1, fast disproportionation reactions regenerate complexes 5 and 1 in a stoichiometric fashion to maintain the ECPB equilibrium.