Polymerization of Allenes by Using an Iron(II) β-Diketiminate Pre-Catalyst to Generate High M
            n Polymers

Callum Woof; Derek J Durand; Ruth Webster

doi:10.1002/chem.202101078

Polymerization of Allenes by Using an Iron(II) β-Diketiminate Pre-Catalyst to Generate High M _n Polymers

Callum Woof, Derek J Durand, Ruth Webster

University of Bristol

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

1 Citation (SciVal)

Abstract

Herein, we report an iron(II)-catalyzed polymerization of arylallenes. This reaction proceeds rapidly at room temperature in the presence of a hydride co-catalyst to generate polymers of weight up to Mn=189 000 Da. We have determined the polymer structure and chain length for a range of monomers through a combination of NMR, differential scanning calorimetry (DSC) and gel permeation chromatography (GPC) analysis. Mechanistically, we postulate that the co-catalyst does not react to form an iron(II) hydride in situ, but instead the chain growth is proceeding via a reactive Fe(III) species. We have also performed kinetic and isotopic experiments to further our understanding. The formation of a highly unusual 1,3-substituted cyclobutane side-product is also investigated.

Original language	English
Pages (from-to)	12335-12340
Number of pages	6
Journal	Chemistry - A European Journal
Volume	27
Issue number	48
Early online date	16 Jul 2021
DOIs	https://doi.org/10.1002/chem.202101078
Publication status	Published - 25 Aug 2021

Bibliographical note

Funding Information:
The EPSRC Centre for Doctoral Training in Catalysis (EP/L016443/1) is thanked for funding (CRW, DJD). The authors would like to thank the MC facility at the University of Bath, in particular Dr. Martin Levere and Dr. Rémi Castaing, for assistance. Many thanks are extended to Dr. Thom McGuire and Dr. Antoine Buchard for helpful discussions and to Dr. Danila Gasperini for preparation of the Fe(I) species. Dr. Adam Squires is thanked for WAXD analysis. 2

Keywords

allenes
cycloaddition
homogeneous catalysis
iron
polymers

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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10.1002/chem.202101078Licence: CC BY

Cite this

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title = "Polymerization of Allenes by Using an Iron(II) β-Diketiminate Pre-Catalyst to Generate High M n Polymers",

abstract = "Herein, we report an iron(II)-catalyzed polymerization of arylallenes. This reaction proceeds rapidly at room temperature in the presence of a hydride co-catalyst to generate polymers of weight up to Mn=189 000 Da. We have determined the polymer structure and chain length for a range of monomers through a combination of NMR, differential scanning calorimetry (DSC) and gel permeation chromatography (GPC) analysis. Mechanistically, we postulate that the co-catalyst does not react to form an iron(II) hydride in situ, but instead the chain growth is proceeding via a reactive Fe(III) species. We have also performed kinetic and isotopic experiments to further our understanding. The formation of a highly unusual 1,3-substituted cyclobutane side-product is also investigated.",

keywords = "allenes, cycloaddition, homogeneous catalysis, iron, polymers",

author = "Callum Woof and Durand, {Derek J} and Ruth Webster",

note = "Funding Information: The EPSRC Centre for Doctoral Training in Catalysis (EP/L016443/1) is thanked for funding (CRW, DJD). The authors would like to thank the MC facility at the University of Bath, in particular Dr. Martin Levere and Dr. R{\'e}mi Castaing, for assistance. Many thanks are extended to Dr. Thom McGuire and Dr. Antoine Buchard for helpful discussions and to Dr. Danila Gasperini for preparation of the Fe(I) species. Dr. Adam Squires is thanked for WAXD analysis. 2 ",

year = "2021",

month = aug,

day = "25",

doi = "10.1002/chem.202101078",

language = "English",

volume = "27",

pages = "12335--12340",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

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T1 - Polymerization of Allenes by Using an Iron(II) β-Diketiminate Pre-Catalyst to Generate High M n Polymers

AU - Woof, Callum

AU - Durand, Derek J

AU - Webster, Ruth

N1 - Funding Information: The EPSRC Centre for Doctoral Training in Catalysis (EP/L016443/1) is thanked for funding (CRW, DJD). The authors would like to thank the MC facility at the University of Bath, in particular Dr. Martin Levere and Dr. Rémi Castaing, for assistance. Many thanks are extended to Dr. Thom McGuire and Dr. Antoine Buchard for helpful discussions and to Dr. Danila Gasperini for preparation of the Fe(I) species. Dr. Adam Squires is thanked for WAXD analysis. 2

PY - 2021/8/25

Y1 - 2021/8/25

N2 - Herein, we report an iron(II)-catalyzed polymerization of arylallenes. This reaction proceeds rapidly at room temperature in the presence of a hydride co-catalyst to generate polymers of weight up to Mn=189 000 Da. We have determined the polymer structure and chain length for a range of monomers through a combination of NMR, differential scanning calorimetry (DSC) and gel permeation chromatography (GPC) analysis. Mechanistically, we postulate that the co-catalyst does not react to form an iron(II) hydride in situ, but instead the chain growth is proceeding via a reactive Fe(III) species. We have also performed kinetic and isotopic experiments to further our understanding. The formation of a highly unusual 1,3-substituted cyclobutane side-product is also investigated.

AB - Herein, we report an iron(II)-catalyzed polymerization of arylallenes. This reaction proceeds rapidly at room temperature in the presence of a hydride co-catalyst to generate polymers of weight up to Mn=189 000 Da. We have determined the polymer structure and chain length for a range of monomers through a combination of NMR, differential scanning calorimetry (DSC) and gel permeation chromatography (GPC) analysis. Mechanistically, we postulate that the co-catalyst does not react to form an iron(II) hydride in situ, but instead the chain growth is proceeding via a reactive Fe(III) species. We have also performed kinetic and isotopic experiments to further our understanding. The formation of a highly unusual 1,3-substituted cyclobutane side-product is also investigated.

KW - allenes

KW - cycloaddition

KW - homogeneous catalysis

KW - iron

KW - polymers

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U2 - 10.1002/chem.202101078

DO - 10.1002/chem.202101078

M3 - Article

SN - 0947-6539

VL - 27

SP - 12335

EP - 12340

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 48

ER -

Polymerization of Allenes by Using an Iron(II) β-Diketiminate Pre-Catalyst to Generate High M _n Polymers

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

Access to Document

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EC Fellowship - Cast Iron Catalysis: New Protocols for the Synthesis of Carbon-Phosphorus Bonds

Cite this

Polymerization of Allenes by Using an Iron(II) β-Diketiminate Pre-Catalyst to Generate High M n Polymers

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Projects

EC Fellowship - Cast Iron Catalysis: New Protocols for the Synthesis of Carbon-Phosphorus Bonds

Cite this

Polymerization of Allenes by Using an Iron(II) β-Diketiminate Pre-Catalyst to Generate High M _n Polymers