TY - JOUR
T1 - Combining acid-base, redox and substrate binding functionalities to give a complete model for the [FeFe]-hydrogenase
AU - Camara, James M.
AU - Rauchfuss, Thomas B.
PY - 2012/1
Y1 - 2012/1
N2 - Some enzymes function by coupling substrate turnover with electron transfer from a redox cofactor such as ferredoxin. In the [FeFe]-hydrogenases, nature's fastest catalysts for the production and oxidation of H 2, the one-electron redox by a ferredoxin complements the one-electron redox by the diiron active site. In this Article, we replicate the function of the ferredoxins with the redox-active ligand Cp*Fe(C 5 Me 4 CH 2 PEt 2) (FcP*). FcP* oxidizes at mild potentials, in contrast to most ferrocene-based ligands, which suggests that it might be a useful mimic of ferredoxin cofactors. The specific model is Fe 2[(SCH 2) 2 NBn](CO) 3 (FcP*)(dppv) (1), which contains the three functional components of the active site: a reactive diiron centre, an amine as a proton relay and, for the first time, a one-electron redox module. By virtue of the synthetic redox cofactor, [1] 2+ exhibits unique reactivity towards hydrogen and CO. In the presence of excess oxidant and base, H 2 oxidation by [1] 2+ is catalytic.
AB - Some enzymes function by coupling substrate turnover with electron transfer from a redox cofactor such as ferredoxin. In the [FeFe]-hydrogenases, nature's fastest catalysts for the production and oxidation of H 2, the one-electron redox by a ferredoxin complements the one-electron redox by the diiron active site. In this Article, we replicate the function of the ferredoxins with the redox-active ligand Cp*Fe(C 5 Me 4 CH 2 PEt 2) (FcP*). FcP* oxidizes at mild potentials, in contrast to most ferrocene-based ligands, which suggests that it might be a useful mimic of ferredoxin cofactors. The specific model is Fe 2[(SCH 2) 2 NBn](CO) 3 (FcP*)(dppv) (1), which contains the three functional components of the active site: a reactive diiron centre, an amine as a proton relay and, for the first time, a one-electron redox module. By virtue of the synthetic redox cofactor, [1] 2+ exhibits unique reactivity towards hydrogen and CO. In the presence of excess oxidant and base, H 2 oxidation by [1] 2+ is catalytic.
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U2 - 10.1038/nchem.1180
DO - 10.1038/nchem.1180
M3 - Article
C2 - 22169868
AN - SCOPUS:83655183063
VL - 4
SP - 26
EP - 30
JO - Nature Chemistry
JF - Nature Chemistry
SN - 1755-4330
IS - 1
ER -