In this lecture we will review challenges and solutions in our efforts to prepare 57Fe-labeled models of the two hydrogenase active sites. One class of targets are of the type (diphosphine)(CO)Fe(SR)2MLn, which can be generated from 57Fe(SR)2(diphosphine)(CO)2, generated via 57Fe2I4(iPrOH)4, obtained from iodination of 57Fe metal. A similar method can be used to give (CO)357Fe(SR)2Ni(dppe), but proceeding via [(CO)357Fe(μ-I)(SR)2Ni(dppe)]+. Work on labeling the diiron center is motivated by the recent report that synthetic [Fe2[(SCH2)2NH)](CN)2(CO)4]2- can be incorporated into an apo-hydrogenase protein. We will review routes to 57Fe2[(S2(CH2)n](CO)6 for n = 2 (efficient) and 3 (inefficient) from 57FeBr2. Finally we will describe new routes that enable incorporation of the azadithiolate cofactor.

Preparation of isotopically labeled active site models for the [FeFe]- and [FeNi]-hydrogenases

249th National Meeting (2015)

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