Chemists are closing in on functional and structural models for the [FeFe] hydrogenases. Oxidation of [Fe2(S2C2H4)(CO)3(PMe3)(dppv)] (dppv=cis-1,2-C2H2(PPh2)2) by one electron affords a mixed-valence model for the Hox state of the active site of the [FeFe] hydrogenases. Like the enzyme, this model exhibits the “rotated structure” and binds CO (see scheme). The radical character of the model is confirmed by its ready binding of NO.
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Justice et al. (2007) studied this question.
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