Ein einkerniger Cobalt‐Komplex mit einem neuartigen fünfzähnigen Liganden (siehe Bild) katalysiert die Entwicklung von Wasserstoff in ausschließlich wässriger Lösung. Der Komplex könnte als Elektro‐ sowie als Photokatalysator zur effizienten Bildung von Wasserstoff verwendet werden.

The ability of cobalt-based transition metal complexes to catalyze electrochemical proton reduction to produce molecular hydrogen has resulted in a large number of mechanistic studies involving various cobalt complexes. While the basic mechanism of proton reduction promoted by cobalt species is well-understood, the reactivity of certain reaction intermediates, such as Co(I) and Co(III)-H, is still relatively unknown owing to their transient nature, especially in aqueous media. In this work we investigate the properties of intermediates produced during catalytic proton reduction in aqueous solutions promoted by the [(DPA-Bpy)Co(OH2)](n+) (DPA-Bpy = N,N-bis(2-pyridinylmethyl)-2,20-bipyridine-6-methanamine) complex ([Co(L)(OH2)](n+) where L is the pentadentate DPA-Bpy ligand or [Co(OH2)](n+) as a shorthand). Experimental results based on transient pulse radiolysis and laser flash photolysis methods, together with electrochemical studies and supported by density functional theory (DFT) calculations indicate that, while the water ligand is strongly coordinated to the metal center in the oxidation state 3+, one-electron reduction of the complex to form a Co(II) species results in weakening the Co-O bond. The further reduction to a Co(I) species leads to the loss of the aqua ligand and the formation of [Co(I)-VS)](+) (VS = vacant site). Interestingly, DFT calculations also predict the existence of a [Co(I)(κ(4)-L)(OH2)](+) species at least transiently, and its formation is consistent with the experimental Pourbaix diagram. Both electrochemical and kinetics results indicate that the Co(I) species must undergo some structural change prior to accepting the proton, and this transformation represents the rate-determining step (RDS) in the overall formation of [Co(III)-H](2+). We propose that this RDS may originate from the slow removal of a solvent ligand in the intermediate [Co(I)(κ(4)-L)(OH2)](+) in addition to the significant structural reorganization of the metal complex and surrounding solvent resulting in a high free energy of activation.

A detailed examination of each step of the reaction sequence in the photochemical sacrificial hydrogen generation system consisting of [Ru(bpy)3](2+)/ascorbate/[Co(DPA-bpy)OH2](3+) was conducted. By clearly defining quenching, charge separation, and back electron transfer in the [Ru(bpy)3](2+)/ascorbate system, the details necessary for evaluation of the efficiency of water reduction with various catalysts are provided. In the particular Co(III) catalyst investigated, it is clear that the light induced catalytic process is considerably less efficient than the electrocatalytic process. A potential source of catalyst inefficiency in this system is reduction of the products formed in oxidation of the sacrificial electron donor. The data provided for excited state quenching and charge separation in this particular aqueous system are meant to be used by others for thorough investigation of the quantum efficiencies of other aqueous homogeneous and nanoheterogeneous catalysts for water reduction.

Ein einkerniger Cobalt‐Komplex mit einem neuartigen fünfzähnigen Liganden (siehe Bild) katalysiert die Entwicklung von Wasserstoff in ausschließlich wässriger Lösung. Der Komplex könnte als Elektro‐ sowie als Photokatalysator zur effizienten Bildung von Wasserstoff verwendet werden.