Abstract
The azadithiolate complex Fe2[(SCH2)26NMe](CO)6 reacts with borane to give an initial 1:1 adduct, which spontaneously decarbonylates to give Fe2[(SCH2)2NMeBH3](CO)5. Featuring a Fe-H-B three-center, two-electron interaction, the pentacarbonyl complex is a structural model for H2 complexes invoked in the [FeFe]-hydrogenases. The pentacarbonyl compound is a "σ complex", where a B-H σ bond serves as a ligand for iron. The structure of this σ complex was characterized by variable-temperature NMR spectroscopy and X-ray crystallography. Complementary to the 1:1 borane adduct is the quaternary ammonium complex [Fe2](SCH2)2NMe2](CO)6]+, which was also characterized. It represents a kinetically robust analogue of the N-protonated amine cofactor, as indicated by its mild reduction potential.
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