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

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80 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

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