[FeFe]-Hydrogenase H-Cluster Mimics with Various -S(CH₂)_nS- Linker Lengths (n = 2-8): A Systematic Study

The effect of the nature of the dithiolato ligand on the physical and electrochemical properties of synthetic H-cluster mimics of the [FeFe]-hydrogenase is still of significant concern. In this report we describe the cyclization of various alkanedithiols to afford cyclic disulfide, tetrasulfide, and hexasulfide compounds. The latter compounds were used as proligands for the synthesis of a series of [FeFe]-hydrogenase H-cluster mimics having the general formulas [Fe₂(CO)₆{μ-S(CH₂)_nS}] (n = 4-8), [Fe₂(CO)₆{μ-S(CH₂)_nS}]₂ (n = 6-8), and [Fe₂(CO)₆{(μ-S(CH₂)_nS)₂}] (n = 6-8). The resulting complexes were characterized by ¹H and ¹³C{¹H} NMR and IR spectroscopic techniques, mass spectrometry, and elemental analysis as well as X-ray analysis. The purpose of this research was to study the influence of the systematic increase of n from 2 to 7 on the redox potentials of the models and the catalytic ability in the presence of acetic acid (AcOH) by applying cyclic voltammetry.