Christopher J Adams,
Robin B Bedford,
Emma Carter,
Nicholas J Gower,
Mairi F Haddow,
Jeremy N Harvey,
Michael Huwe, M Ángeles Cartes,
Stephen M Mansell,
Carla Mendoza,
Damien M Murphy,
Emily C Neeve,
Joshua Nunn
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ABSTRACT: 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.
Journal of the American Chemical Society 06/2012; 134(25):10333-6. · 9.91 Impact Factor