Characterization of a Borane σ Complex of a Diiron Dithiolate: Model for an Elusive Dihydrogen Adduct

The azadithiolate complex Fe2[(SCH2)2NMe]­(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.