Iron Catalyzed Double Bond Isomerization: Evidence for an FeI/FeIII Catalytic Cycle

Callum R Woof; Derek J Durand; Natalie Fey; Emma Richards; Ruth L Webster

doi:10.1002/chem.202004980

Iron Catalyzed Double Bond Isomerization: Evidence for an FeI/FeIII Catalytic Cycle

Callum R Woof, Derek J Durand, Natalie Fey^*, Emma Richards^*, Ruth L Webster^*

^*Corresponding author for this work

Research output: Contribution to journal › Article (Academic Journal) › peer-review

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Abstract

Iron-catalyzed isomerization of alkenes is reported using an iron(II) β-diketiminate pre-catalyst. The reaction proceeds with a catalytic amount of a hydride source, such as pinacol borane (HBpin) or ammonia borane (H 3 N·BH 3 ). Reactivity with both allyl arenes and aliphatic alkenes has been studied. The catalytic mechanism was investigated by a variety of means, including deuteration studies, Density Functional Theory (DFT) and Electron Paramagnetic Resonance (EPR) spectroscopy. The data obtained support a pre-catalyst activation step that gives access to an η 2 -coordinated alkene Fe(I) complex, followed by oxidative addition of the alkene to give an Fe(III) intermediate, which then undergoes reductive elimination to allow release of the isomerization product.

Original language	English
Pages (from-to)	5972-5977
Number of pages	6
Journal	Chemistry - A European Journal
Volume	27
Issue number	19
Early online date	15 Mar 2021
DOIs	https://doi.org/10.1002/chem.202004980
Publication status	Published - 1 Apr 2021

Keywords

isomerization
redox chemistry
iron
reaction mechanism
homogeneous catalysis

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title = "Iron Catalyzed Double Bond Isomerization: Evidence for an FeI/FeIII Catalytic Cycle",

abstract = "Iron-catalyzed isomerization of alkenes is reported using an iron(II) β-diketiminate pre-catalyst. The reaction proceeds with a catalytic amount of a hydride source, such as pinacol borane (HBpin) or ammonia borane (H 3 N·BH 3 ). Reactivity with both allyl arenes and aliphatic alkenes has been studied. The catalytic mechanism was investigated by a variety of means, including deuteration studies, Density Functional Theory (DFT) and Electron Paramagnetic Resonance (EPR) spectroscopy. The data obtained support a pre-catalyst activation step that gives access to an η 2 -coordinated alkene Fe(I) complex, followed by oxidative addition of the alkene to give an Fe(III) intermediate, which then undergoes reductive elimination to allow release of the isomerization product.",

keywords = "isomerization, redox chemistry, iron, reaction mechanism, homogeneous catalysis",

author = "Woof, {Callum R} and Durand, {Derek J} and Natalie Fey and Emma Richards and Webster, {Ruth L}",

note = "{\textcopyright} 2021 Wiley-VCH GmbH.",

year = "2021",

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day = "1",

doi = "10.1002/chem.202004980",

language = "English",

volume = "27",

pages = "5972--5977",

journal = "Chemistry - A European Journal",

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publisher = "Wiley-VCH Verlag",

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TY - JOUR

T1 - Iron Catalyzed Double Bond Isomerization

T2 - Evidence for an FeI/FeIII Catalytic Cycle

AU - Woof, Callum R

AU - Durand, Derek J

AU - Fey, Natalie

AU - Richards, Emma

AU - Webster, Ruth L

PY - 2021/4/1

Y1 - 2021/4/1

N2 - Iron-catalyzed isomerization of alkenes is reported using an iron(II) β-diketiminate pre-catalyst. The reaction proceeds with a catalytic amount of a hydride source, such as pinacol borane (HBpin) or ammonia borane (H 3 N·BH 3 ). Reactivity with both allyl arenes and aliphatic alkenes has been studied. The catalytic mechanism was investigated by a variety of means, including deuteration studies, Density Functional Theory (DFT) and Electron Paramagnetic Resonance (EPR) spectroscopy. The data obtained support a pre-catalyst activation step that gives access to an η 2 -coordinated alkene Fe(I) complex, followed by oxidative addition of the alkene to give an Fe(III) intermediate, which then undergoes reductive elimination to allow release of the isomerization product.

AB - Iron-catalyzed isomerization of alkenes is reported using an iron(II) β-diketiminate pre-catalyst. The reaction proceeds with a catalytic amount of a hydride source, such as pinacol borane (HBpin) or ammonia borane (H 3 N·BH 3 ). Reactivity with both allyl arenes and aliphatic alkenes has been studied. The catalytic mechanism was investigated by a variety of means, including deuteration studies, Density Functional Theory (DFT) and Electron Paramagnetic Resonance (EPR) spectroscopy. The data obtained support a pre-catalyst activation step that gives access to an η 2 -coordinated alkene Fe(I) complex, followed by oxidative addition of the alkene to give an Fe(III) intermediate, which then undergoes reductive elimination to allow release of the isomerization product.

KW - isomerization

KW - redox chemistry

KW - iron

KW - reaction mechanism

KW - homogeneous catalysis

U2 - 10.1002/chem.202004980

DO - 10.1002/chem.202004980

M3 - Article (Academic Journal)

C2 - 33492679

SN - 0947-6539

VL - 27

SP - 5972

EP - 5977

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 19

ER -

Iron Catalyzed Double Bond Isomerization: Evidence for an FeI/FeIII Catalytic Cycle

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