Pentanuclear Scaffold: A Molecular Platform for Small-Molecule Conversions

Small-molecule conversions involving multielectron transfer processes enable the conversion of earth-abundant materials into valuable chemicals and are regarded as a solution for environmental and energy shortage problems. In this context, the development of artificial catalysts that promote these reactions is an important research target. In nature, metalloenzymes that contain multinuclear metal complexes as active sites are known to efficiently catalyze reactions under mild conditions. Therefore, using multinudear metal complexes as artificial catalysts can be an attractive strategy for small-molecule conversions involving multielectron transfer processes. However, multinudear-metal-complex-based catalysts for these reactions have not been well established. In this Account, we describe our recent advances in the development of multinudear metal complexes as catalysts for smallmolecule conversion, mainly focusing on water oxidation. As small-molecule conversions tob,trate involving multielectron transfer processes consists of two essential processes, (1) the transfer binding of multiple electrons and (2) the formation/cleavage of covalent bond(s), catalysts for these reactions should facilitate both steps. Therefore, we assumed that the assembly of redox-active metal ions and the cooperative effect of neighboring coordinatively unsaturated metal ions can promote these processes. On the basis of this assumption, we employed a pentanuclear metal complex as a molecular scaffold for the catalyst. The scaffold has a pentanuclear structure with quasi-D-3 symmetry and consists of a [M-3(mu(3)-X)] core (X = O2- or OH-) wrapped by two [M(mu-bpp)(3)] units (Hbpp = 3,5-bis(2-pyridyl)pyrazole). The metal ions in the triangular core are coordinatively unsaturated, whereas the metal ions at the apical positions are coordinatively saturated. In other words, the pentanuclear scaffold possesses multiple redox-active centers and coordinatively unsaturated sites. It should also be noted that the electron transfer ability of the complex changes dramatically depending on the identity of the constituent metal ions. The iron derivative of the pentanuclear scaffold was found to serve as an electrocatalyst for water oxidation (2H(2)O -> O-2 + 4e(-) + 4H(+)) with a high reaction rate and excellent robustness. The substitution of metal ions in the pentanuclear scaffold to cobalt ions resulted in the development of a catalyst for CO2 reduction. Furthermore, we investigated the effect of substituents on the ligands of the pentanuclear iron complex and succeeded in precisely manipulating the electron transfer possess. These results clearly demonstrate that the pentanudear scaffold is an attractive platform for catalysts for small-molecule conversions. Additionally, the intrinsic features of the multinuclear catalytic system, which are totally different from those of conventional mononuclear-metal-complex-based catalysts, are disclosed. In reactions mediated by multinuclear complexes, the multinudear core can initially accumulate the charge required for catalysis to reach the catalytically active state. Subsequently, the catalyst in the active state reacts with the substrate, initiating electron transfer to the substrate and rearrangement of covalent bonds in the substrate to afford the product. In such a mechanism, the desired number of electrons can be transferred to the substrates in an on-demand fashion, and the formation of undesired chemical species in the targeted catalysis may be prevented. This feature of multinudear-metal-complex-based catalysts will achieve demanding small-molecule conversions with a high reaction rate, selectivity, and durability.