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.
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, UK.
Christopher J
CJ
Adams
Robin B
RB
Bedford
Emma
E
Carter
Nicholas J
NJ
Gower
Mairi F
MF
Haddow
Jeremy N
JN
Harvey
Michael
M
Huwe
M Ángeles
MÁ
Cartes
Stephen M
SM
Mansell
Carla
C
Mendoza
Damien M
DM
Murphy
Emily C
EC
Neeve
Joshua
J
Nunn
D002384:Catalysis; D018360:Crystallography, X-Ray; D007501:Iron / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D009942:Organometallic Compounds; D007501:Iron