Iron(I) in Negishi Cross-Coupling Reactions

Herein we demonstrate both the importance of Fe­(I) in Negishi cross-coupling reactions with arylzinc reagents and the isolation of catalytically competent Fe­(I) intermediates. These complexes, [FeX­(dpbz)2] [X = 4-tolyl (7), Cl (8a), Br (8b); dpbz = 1,2-bis­(diphenylphosphino)­benzene], were characterized by crystallography and tested for activity in representative reactions. The complexes are low-spin with no significant spin density on the ligands. While complex 8b shows performance consistent with an on-cycle intermediate, it seems that 7 is an off-cycle species.