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The Mo nitrogenase catalyzes the ambient reduction of N2 to NH3 at its M‐cluster site. A complex metallocofactor with a core composition of [MoFe7S9C], the M‐cluster, can be extracted from the protein scaffold and used to facilitate the catalytic reduction of CN−, CO, and CO2 into hydrocarbons in the isolated state. Herein, we report the synthesis, structure, and reactivity of an asymmetric M‐cluster...
Nitrogenase catalyzes substrate reduction at its cofactor center ([(Cit)MoFe7S9C]n−; designated M‐cluster). Here, we report the formation of an artificial, nitrogenase‐mimicking enzyme upon insertion of a synthetic model complex ([Fe6S9(SEt)2]4−; designated Fe6RHH) into the catalytic component of nitrogenase (designated NifDKapo). Two Fe6RHH clusters were inserted into NifDKapo, rendering the conformation...
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