Di-cobalt(ii) catalysts for the copolymerisation of CO2 and cyclohexene oxide: support for a dinuclear mechanism?

Michael R. Kember, Fabian Jutz, Antoine Buchard, Andrew J. P. White, Charlotte K. Williams

Research output: Contribution to journalArticle

69 Citations (Scopus)

Abstract

The synthesis and characterisation of a series of di-cobalt(ii) halide complexes, coordinated by a macrocyclic ancillary ligand, is reported. The new complexes show excellent activity as catalysts for the copolymerisation of cyclohexene oxide (CHO) and carbon dioxide, under just 1 atmosphere of pressure of CO2. The complexation of a series of co-ligands has been investigated, including nucleophiles of varying strength, (4-dimethylaminopyridine (DMAP), N-methylimidazole (MeIm) and pyridine), and the anionic donor (Cl) from bulky ammonium salts, ([HNEt3]Cl, [DBU-H]Cl and [MTBD-H]Cl). Structure-activity studies of the complexes, including X-ray crystallography data, in conjunction with mass spectrometry experiments, are used to support a proposed dinuclear mechanism. The initial rate of copolymerisation, determined using in situ attenuated total reflectance infrared (ATR-IR) spectroscopy, shows a first order dependence on both the catalyst concentration and the concentration of cyclohexene oxide. A dinuclear mechanism is proposed in which catalysis occurs on the convex face of the molecule, leading to chain growth from a single site.
Original languageEnglish
Pages (from-to)1245-1255
Number of pages11
JournalChemical Science
Volume3
Issue number4
Early online date6 Feb 2012
DOIs
Publication statusPublished - 1 Apr 2012

Fingerprint

Carbon Monoxide
Cobalt
Copolymerization
Ligands
Nucleophiles
Catalysts
X ray crystallography
Complexation
Ammonium Compounds
Carbon Dioxide
Catalysis
Mass spectrometry
Infrared spectroscopy
Salts
Molecules
Experiments
cyclohexene oxide
1-methylimidazole
pyridine
4-dimethylaminopyridine

Cite this

Di-cobalt(ii) catalysts for the copolymerisation of CO2 and cyclohexene oxide: support for a dinuclear mechanism? / Kember, Michael R.; Jutz, Fabian; Buchard, Antoine; White, Andrew J. P.; Williams, Charlotte K.

In: Chemical Science, Vol. 3, No. 4, 01.04.2012, p. 1245-1255.

Research output: Contribution to journalArticle

Kember, Michael R. ; Jutz, Fabian ; Buchard, Antoine ; White, Andrew J. P. ; Williams, Charlotte K. / Di-cobalt(ii) catalysts for the copolymerisation of CO2 and cyclohexene oxide: support for a dinuclear mechanism?. In: Chemical Science. 2012 ; Vol. 3, No. 4. pp. 1245-1255.
@article{b36511e7a3834162ad27b964ca6040d4,
title = "Di-cobalt(ii) catalysts for the copolymerisation of CO2 and cyclohexene oxide: support for a dinuclear mechanism?",
abstract = "The synthesis and characterisation of a series of di-cobalt(ii) halide complexes, coordinated by a macrocyclic ancillary ligand, is reported. The new complexes show excellent activity as catalysts for the copolymerisation of cyclohexene oxide (CHO) and carbon dioxide, under just 1 atmosphere of pressure of CO2. The complexation of a series of co-ligands has been investigated, including nucleophiles of varying strength, (4-dimethylaminopyridine (DMAP), N-methylimidazole (MeIm) and pyridine), and the anionic donor (Cl) from bulky ammonium salts, ([HNEt3]Cl, [DBU-H]Cl and [MTBD-H]Cl). Structure-activity studies of the complexes, including X-ray crystallography data, in conjunction with mass spectrometry experiments, are used to support a proposed dinuclear mechanism. The initial rate of copolymerisation, determined using in situ attenuated total reflectance infrared (ATR-IR) spectroscopy, shows a first order dependence on both the catalyst concentration and the concentration of cyclohexene oxide. A dinuclear mechanism is proposed in which catalysis occurs on the convex face of the molecule, leading to chain growth from a single site.",
author = "Kember, {Michael R.} and Fabian Jutz and Antoine Buchard and White, {Andrew J. P.} and Williams, {Charlotte K.}",
year = "2012",
month = "4",
day = "1",
doi = "10.1039/C2SC00802E",
language = "English",
volume = "3",
pages = "1245--1255",
journal = "Chemical Science",
issn = "2041-6520",
publisher = "Royal Society of Chemistry",
number = "4",

}

TY - JOUR

T1 - Di-cobalt(ii) catalysts for the copolymerisation of CO2 and cyclohexene oxide: support for a dinuclear mechanism?

AU - Kember, Michael R.

AU - Jutz, Fabian

AU - Buchard, Antoine

AU - White, Andrew J. P.

AU - Williams, Charlotte K.

PY - 2012/4/1

Y1 - 2012/4/1

N2 - The synthesis and characterisation of a series of di-cobalt(ii) halide complexes, coordinated by a macrocyclic ancillary ligand, is reported. The new complexes show excellent activity as catalysts for the copolymerisation of cyclohexene oxide (CHO) and carbon dioxide, under just 1 atmosphere of pressure of CO2. The complexation of a series of co-ligands has been investigated, including nucleophiles of varying strength, (4-dimethylaminopyridine (DMAP), N-methylimidazole (MeIm) and pyridine), and the anionic donor (Cl) from bulky ammonium salts, ([HNEt3]Cl, [DBU-H]Cl and [MTBD-H]Cl). Structure-activity studies of the complexes, including X-ray crystallography data, in conjunction with mass spectrometry experiments, are used to support a proposed dinuclear mechanism. The initial rate of copolymerisation, determined using in situ attenuated total reflectance infrared (ATR-IR) spectroscopy, shows a first order dependence on both the catalyst concentration and the concentration of cyclohexene oxide. A dinuclear mechanism is proposed in which catalysis occurs on the convex face of the molecule, leading to chain growth from a single site.

AB - The synthesis and characterisation of a series of di-cobalt(ii) halide complexes, coordinated by a macrocyclic ancillary ligand, is reported. The new complexes show excellent activity as catalysts for the copolymerisation of cyclohexene oxide (CHO) and carbon dioxide, under just 1 atmosphere of pressure of CO2. The complexation of a series of co-ligands has been investigated, including nucleophiles of varying strength, (4-dimethylaminopyridine (DMAP), N-methylimidazole (MeIm) and pyridine), and the anionic donor (Cl) from bulky ammonium salts, ([HNEt3]Cl, [DBU-H]Cl and [MTBD-H]Cl). Structure-activity studies of the complexes, including X-ray crystallography data, in conjunction with mass spectrometry experiments, are used to support a proposed dinuclear mechanism. The initial rate of copolymerisation, determined using in situ attenuated total reflectance infrared (ATR-IR) spectroscopy, shows a first order dependence on both the catalyst concentration and the concentration of cyclohexene oxide. A dinuclear mechanism is proposed in which catalysis occurs on the convex face of the molecule, leading to chain growth from a single site.

UR - http://www.scopus.com/inward/record.url?scp=84858018612&partnerID=8YFLogxK

UR - http://dx.doi.org/10.1039/C2SC00802E

U2 - 10.1039/C2SC00802E

DO - 10.1039/C2SC00802E

M3 - Article

VL - 3

SP - 1245

EP - 1255

JO - Chemical Science

JF - Chemical Science

SN - 2041-6520

IS - 4

ER -