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Issue 35, 2012
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Reductive functionalization of carbon dioxide to methyl acrylate at zerovalent tungsten

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Abstract

Alkali metal reduction of tungsten tetrachloride in the presence of excess trimethylphosphite and ethylene affords moderate yields of trans-tetrakis(trimethylphosphite)tungsten bis(ethylene). This easily prepared species bearing inexpensive ancillary ligands promotes the oxidative coupling of carbon dioxide and ethylene at ambient temperature to produce two isomeric tetrakis(trimethylphosphite)tungsten acrylate hydride complexes. These isomers vary by the κ2-O,O and κ3-C,C,O coordination mode of the acrylate ligand, and swiftly interconvert in solution as detected by 2D NMR spectroscopy. The CO2-derived acrylate fragment may be released from the tungsten coordination sphere by treatment with methyl iodide to afford modest quantities of free methyl acrylate.

Graphical abstract: Reductive functionalization of carbon dioxide to methyl acrylate at zerovalent tungsten

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Publication details

The article was received on 11 May 2012, accepted on 24 Jun 2012 and first published on 31 Jul 2012


Article type: Paper
DOI: 10.1039/C2DT31032E
Citation: Dalton Trans., 2012,41, 10763-10768
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    Reductive functionalization of carbon dioxide to methyl acrylate at zerovalent tungsten

    J. M. Wolfe and W. H. Bernskoetter, Dalton Trans., 2012, 41, 10763
    DOI: 10.1039/C2DT31032E

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