Iron(I) in Negishi cross-coupling reactions

Christopher J Adams; Robin B Bedford; Emma Carter; Nicholas J Gower; Mairi F Haddow; Jeremy N Harvey; Michael Huwe; M Angeles Cartes; Stephen M Mansell; Carla Mendoza; Damien M Murphy; Emily C Neeve; Joshua Nunn

doi:10.1021/ja303250t

Iron(I) in Negishi cross-coupling reactions

Christopher J Adams, Robin B Bedford, Emma Carter, Nicholas J Gower, Mairi F Haddow, Jeremy N Harvey, Michael Huwe, M Angeles Cartes, Stephen M Mansell, Carla Mendoza, Damien M Murphy, Emily C Neeve, Joshua Nunn

Research output: Contribution to journal › Article › peer-review

162 Citations (Scopus)

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.

Original language	English
Pages (from-to)	10333-10336
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	134
Issue number	25
DOIs	https://doi.org/10.1021/ja303250t
Publication status	Published - 27 Jun 2012

Keywords

ALKYL-HALIDES
GRIGNARD REAGENTS
COMPLEXES
LIGAND
REACTIVITY
CATALYSIS

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10.1021/ja303250t

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title = "Iron(I) in Negishi cross-coupling reactions",

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.",

keywords = "ALKYL-HALIDES, GRIGNARD REAGENTS, COMPLEXES, LIGAND, REACTIVITY, CATALYSIS",

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year = "2012",

month = jun,

day = "27",

doi = "10.1021/ja303250t",

language = "English",

volume = "134",

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journal = "Journal of the American Chemical Society",

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T1 - Iron(I) in Negishi cross-coupling reactions

AU - Adams, Christopher J

AU - Bedford, Robin B

AU - Carter, Emma

AU - Gower, Nicholas J

AU - Haddow, Mairi F

AU - Harvey, Jeremy N

AU - Huwe, Michael

AU - Angeles Cartes, M

AU - Mansell, Stephen M

AU - Mendoza, Carla

AU - Murphy, Damien M

AU - Neeve, Emily C

AU - Nunn, Joshua

PY - 2012/6/27

Y1 - 2012/6/27

N2 - 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.

AB - 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.

KW - ALKYL-HALIDES

KW - GRIGNARD REAGENTS

KW - COMPLEXES

KW - LIGAND

KW - REACTIVITY

KW - CATALYSIS

U2 - 10.1021/ja303250t

DO - 10.1021/ja303250t

M3 - Article

C2 - 22694754

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SP - 10333

EP - 10336

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 25

ER -

Iron(I) in Negishi cross-coupling reactions

Abstract

Keywords

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