Electrocatalytic [FeFe]-hydrogenase mimics for the hydrogen evolution reaction (HER) generally suffer from low activity, high overpotential, aggregation, oxygen sensitivity, and low solubility in water. By using atom-transfer radical polymerization (ATRP), a new class of [FeFe]-metallopolymers with precise molar mass, defined composition, and low polydispersity, has been prepared. The synthetic methodology introduced here allows facile variation of polymer composition to optimize the [FeFe] solubility, activity, and long-term chemical and aerobic stability. Water soluble functional metallopolymers facilitate electrocatalytic hydrogen production in neutral water with loadings as low as 2 ppm and operate at rates an order of magnitude faster than hydrogenases (2.5×10 s ), and with low overpotential requirement. Furthermore, unlike the hydrogenases, these systems are insensitive to oxygen during catalysis, with turnover numbers on the order of 40 000 under both anaerobic and aerobic conditions.

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 H2 production.

Small-molecule catalysts inspired by the active sites of [FeFe]-hydrogenase enzymes have long struggled to achieve fast rates of hydrogen evolution, long-term stability, water solubility, and oxygen compatibility. We profoundly improved on these deficiencies by grafting polymers from a metalloinitiator containing a [2Fe-2S] moiety to form water-soluble poly­(2-dimethylamino)­ethyl methacrylate metallopolymers (PDMAEMA-g-[2Fe-2S]) using atom transfer radical polymerization (ATRP). This study illustrates the critical role of the polymer composition in enhancing hydrogen evolution and aerobic stability by comparing the catalytic activity of PDMAEMA-g-[2Fe-2S] with a nonionic water-soluble metallopolymer based on poly­(oligo­(ethylene glycol) methacrylate) prepared via ATRP (POEGMA-g-[2Fe-2S]) with the same [2Fe-2S] metalloinitiator. Additionally, the tunability of catalyst activity is demonstrated by the synthesis of metallocopolymers incorporating the 2-(dimethylamino)­ethyl methacrylate (DMAEMA) and oligo­(ethylene glycol) methacrylate (OEGMA) monomers. Electrochemical investigations into these metallo­(co)­polymers show that PDMAEMA-g-[2Fe-2S] retains complete aerobic stability with catalytic current densities in excess of 20 mA·cm–2, while POEGMA-g-[2Fe-2S] fails to reach 1 mA·cm–2 current density even with the application of high overpotentials (η > 0.8 V) and loses all activity in the presence of oxygen. Random copolymers of the two monomers polymerized with the same [2Fe-2S] initiator showed intermediate activity in terms of current density, overpotential, and aerobic stability.

The redox characteristics of (μ-SMe) 2 Fe 2 (CO) 6 from the 1+ to 2− charge states are reported. This [2Fe-2S] compound is related to the active sites of [FeFe]-hydrogenases but notably without a linker between the sulfur atoms. The 1+ charge state was studied both by ionization in the gas phase by photoelectron spectroscopy and by oxidation in the solution phase by cyclic voltammetry. The adiabatic ionization is to a cation whose structure features a semibridging carbonyl, similar to the structure of the active site of [FeFe]-hydrogenases in the same oxidation state. The reduction of the compound by cyclic voltammetry gives an electrochemically irreversible cathodic peak, which often suggests disproportionation or other irreversible chemical processes in this class of molecules. However, the return scan through electrochemically irreversible oxidation peaks that occur at potentials around 1 V more positive than the reduction led to the recovery of the initial neutral compound. The dependence of the CVs on scan rate, IR spectroelectrochemistry of reduction and oxidation cycles, chronocoulometry, and DFT computations indicate a mechanism in which stabilization of the dianion plays a key role. Initial one-electron reduction of the compound is accompanied in the same cathodic peak with a second slower electron reduction to the dianion. Geometric reorganization and solvation stabilize the [2Fe-2S] 2− dianion such that the potential for addition of the second electron is slightly less negative than that of the first (potential inversion). The return oxidation peaks at more positive potentials follow from rapid pairing of the dianion with another neutral molecule in solution (termed homoassociation) to form a stabilized [4Fe-4S] 2− dianion. Two one-electron oxidations of this [4Fe-4S] 2− dianion result in regeneration of the initial neutral compound. The implications of this homoassociation for the [FeFe]-hydrogenase enzyme, in which the H-cluster active site features a [2Fe-2S] site associated with a [4Fe-4S] cubane cluster via a thiolate bridge, are discussed.

Electrocatalytic [FeFe]-hydrogenase mimics for the hydrogen evolution reaction (HER) generally suffer from low activity,h igh overpotential, aggregation, oxygen sensitivity, and low solubility in water.B yu sing atom-transfer radical polymerization (ATRP), an ew class of [FeFe]-metallopolymers with precise molar mass,d efined composition, and low polydispersity,h as been prepared. The synthetic methodology introduced here allows facile variation of polymer composition to optimize the [FeFe] solubility,a ctivity,a nd long-term chemical and aerobic stability.W ater soluble functional metallopolymers facilitate electrocatalytic hydrogen production in neutral water with loadings as low as 2ppm and operate at rates an order of magnitude faster than hydrogenases (2.5 10 5 s À1 ), and with lowoverpotential requirement. Furthermore, unlike the hydrogenases,these systems are insensitive to oxygen during catalysis,with turnover numbers on the order of 40 000 under both anaerobic and aerobic conditions.