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Issue 5, 2014
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Uptake of one and two molecules of CO2 by the molybdate dianion: a soluble, molecular oxide model system for carbon dioxide fixation

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Abstract

Tetrahedral [MoO4]2− readily binds CO2 at room temperature to produce a robust monocarbonate complex, [MoO32-CO3)]2−, that does not release CO2 even at modestly elevated temperatures (up to 56 °C in solution and 70 °C in the solid state). In the presence of excess carbon dioxide, a second molecule of CO2 binds to afford a pseudo-octahedral dioxo dicarbonate complex, [MoO22-CO3)2]2−, the first structurally characterized transition-metal dicarbonate complex derived from CO2. The monocarbonate [MoO32-CO3)]2− reacts with triethylsilane in acetonitrile under an atmosphere of CO2 to produce formate (69% isolated yield) together with silylated molybdate (quantitative conversion to [MoO3(OSiEt3)], 50% isolated yield) after 22 hours at 85 °C. This system thus illustrates both the reversible binding of CO2 by a simple transition-metal oxoanion and the ability of the latter molecular metal oxide to facilitate chemical CO2 reduction.

Graphical abstract: Uptake of one and two molecules of CO2 by the molybdate dianion: a soluble, molecular oxide model system for carbon dioxide fixation

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Publication details

The article was received on 13 Jan 2014, accepted on 05 Feb 2014 and first published on 05 Feb 2014


Article type: Edge Article
DOI: 10.1039/C4SC00132J
Citation: Chem. Sci., 2014,5, 1772-1776
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    Uptake of one and two molecules of CO2 by the molybdate dianion: a soluble, molecular oxide model system for carbon dioxide fixation

    I. Knopf, T. Ono, M. Temprado, D. Tofan and C. C. Cummins, Chem. Sci., 2014, 5, 1772
    DOI: 10.1039/C4SC00132J

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