Iron Phosphine Catalyzed Cross-Coupling of Tetraorganoborates and Related Group 13 Nucleophiles with Alkyl Halides

Iron phosphine complexes prove to be good precatalysts for the cross-coupling of alkyl, benzyl, and allyl halides with not only aryl triorganoborate salts but also related aluminum-, gallium-, indium-, and thallium-based nucleophiles. Mechanistic studies revealed that while Fe­(I) can be accessed on catalytically relevant time scales, lower average oxidation states are not formed fast enough to be relevant to catalysis. EPR spectroscopic studies reveal the presence of bis­(diphosphine)­iron­(I) complexes in representative catalytic reactions and related processes with a range of group 13 nucleophiles. Isolated examples were studied by Mössbauer spectroscopy and single-crystal X-ray structural analysis, while the electronic structure was probed by dispersion-corrected B3LYP DFT calculations. An EPR study on an iron system with a bulky diphosphine ligand revealed the presence of an S = 1/2 species consistent with the formation of a mono­(diphosphine)­iron­(I) species with inequivalent phosphine donor environments. DFT analysis of model complexes allowed us to rule out a T-shaped Fe­(I) structure, as this is predicted to be high spin.