Controlled radical polymerization of styrene‐based models of the active site of the [FeFe]‐hydrogenase

Abstract Within this study, we report on the first controlled radical polymerization of styrene‐based models of the active site of the [FeFe]‐hydrogenase. Three different model complexes based on styrene were prepared including propanedithiolato‐bridged, 2‐azapropanedithiolato‐bridged, and bifunctional styrene iron complex. These model complexes were copolymerized with styrene using free radical and the reversible addition‐fragmentation chain transfer polymerization method. The polymerization behavior of the hydrogenase models is discussed and analyzed in detail. It could be shown that the model complex can be incorporated into copolymers. The obtained copolymers exhibit narrow molar mass distributions. The presence of the [FeFe]‐hydrogenase models were proven by atomic absorption spectrometry, NMR and IR spectroscopy as well as cyclovoltammetric measurements. It could be shown that the [FeFe]‐hydrogenase mimic copolymers, as well as the monomeric originating complexes exhibit electrocatalytic proton reduction at a low potential of –2.2 V. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013