Catalytic Metallopolymers from [2Fe-2S] Clusters: Artificial Metalloenzymes for Hydrogen Production.

Reviewed herein is the development of novel polymer-supported [2Fe-2S] catalyst systems for electrocatalytic and photocatalytic hydrogen evolution reactions. [FeFe] hydrogenases are the best known naturally occurring metalloenzymes for hydrogen generation, and small-molecule, [2Fe-2S]-containing mimetics of the active site (H-cluster) of these metalloenzymes have been synthesized for years. These small [2Fe-2S] complexes have not yet reached the same capacity as that of enzymes for hydrogen production. Recently, modern polymer chemistry has been utilized to construct an outer coordination sphere around the [2Fe-2S] clusters to provide site isolation, water solubility, and improved catalytic activity. In this review, the various macromolecular motifs and the catalytic properties of these polymer-supported [2Fe-2S] materials are surveyed. The most recent catalysts that incorporate a single [2Fe-2S] complex, termed single-site [2Fe-2S] metallopolymers, exhibit superior activity for H production.