Uptake of one and two molecules of CO[subscript 2] by the molybdate dianion: a soluble, molecular oxide model system for carbon dioxide fixation
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Author(s)
Knopf, Ioana
Ono, Takashi
Temprado, Manuel
Tofan, Daniel
Cummins, Christopher C.
Alternative Title
Uptake of one and two molecules of CO2 by the molybdate dianion: a soluble, molecular oxide model system for carbon dioxide fixation
Date Issued
2014
Journal
Chemical Science
Publisher
Royal Society of Chemistry
Citation
Knopf, Ioana, Takashi Ono, Manuel Temprado, Daniel Tofan, and Christopher C. Cummins. “Uptake of One and Two Molecules of CO[subscript 2] by the Molybdate Dianion: a Soluble, Molecular Oxide Model System for Carbon Dioxide Fixation.” Chemical Science 5, no. 5 (2014): 1772-1776.
Version
Final published version
Abstract
Tetrahedral [MoO4][superscript 2−] readily binds CO[subscript 2] at room temperature to produce a robust monocarbonate complex, [MoO[subscript 3](κ[superscript 2]-CO[subscript 3])][superscript 2−], that does not release CO[subscript 2] 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 CO[subscript 2] binds to afford a pseudo-octahedral dioxo dicarbonate complex, [MoO[subscript 2](κ[superscript 2]-CO[subscript 3])[subscript 2][superscript 2−], the first structurally characterized transition-metal dicarbonate complex derived from CO[subscript 2]. The monocarbonate [MoO[subscript 3](κ[superscript 2]-CO[subscript 3])][superscript 2−] reacts with triethylsilane in acetonitrile under an atmosphere of CO[subscript 2] to produce formate (69% isolated yield) together with silylated molybdate (quantitative conversion to [MoO[subscript 3](OSiEt[subscript 3])][superscript −], 50% isolated yield) after 22 hours at 85 °C. This system thus illustrates both the reversible binding of CO[subscript 2] by a simple transition-metal oxoanion and the ability of the latter molecular metal oxide to facilitate chemical CO[subscript 2] reduction.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1039/c4sc00132j
