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Ligand-induced substrate steering and reshaping of [Ag2(H)]+ scaffold for selective CO2 extrusion from formic acid

Author

Listed:
  • Athanasios Zavras

    (School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne
    ARC Centre of Excellence for Free Radical Chemistry and Biotechnology)

  • George N. Khairallah

    (School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne
    ARC Centre of Excellence for Free Radical Chemistry and Biotechnology)

  • Marjan Krstić

    (Center of Excellence for Science and Technology – Integration of Mediterranean region (STIM) at Interdisciplinary Center for Advanced Science and Technology (ICAST), University of Split)

  • Marion Girod

    (Institut des Sciences Analytiques, Université de Lyon, Université Lyon 1-CNRS-ENS Lyon)

  • Steven Daly

    (Institut Lumière Matière, Université Lyon 1-CNRS, Université de Lyon)

  • Rodolphe Antoine

    (Institut Lumière Matière, Université Lyon 1-CNRS, Université de Lyon)

  • Philippe Maitre

    (Laboratoire de Chimie Physique, Bâtiment 349, Université Paris-Sud, CNRS, Université Paris-Saclay)

  • Roger J. Mulder

    (CSIRO Manufacturing)

  • Stefanie-Ann Alexander

    (School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne
    ARC Centre of Excellence for Free Radical Chemistry and Biotechnology)

  • Vlasta Bonačić-Koutecký

    (Center of Excellence for Science and Technology – Integration of Mediterranean region (STIM) at Interdisciplinary Center for Advanced Science and Technology (ICAST), University of Split
    Humboldt-Universität Berlin, Institut für Chemie)

  • Philippe Dugourd

    (Institut Lumière Matière, Université Lyon 1-CNRS, Université de Lyon)

  • Richard A. J. O’Hair

    (School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne
    ARC Centre of Excellence for Free Radical Chemistry and Biotechnology)

Abstract

Metalloenzymes preorganize the reaction environment to steer substrate(s) along the required reaction coordinate. Here, we show that phosphine ligands selectively facilitate protonation of binuclear silver hydride cations, [LAg2(H)]+ by optimizing the geometry of the active site. This is a key step in the selective, catalysed extrusion of carbon dioxide from formic acid, HO2CH, with important applications (for example, hydrogen storage). Gas-phase ion-molecule reactions, collision-induced dissociation (CID), infrared and ultraviolet action spectroscopy and computational chemistry link structure to reactivity and mechanism. [Ag2(H)]+ and [Ph3PAg2(H)]+ react with formic acid yielding Lewis adducts, while [(Ph3P)2Ag2(H)]+ is unreactive. Using bis(diphenylphosphino)methane (dppm) reshapes the geometry of the binuclear Ag2(H)+ scaffold, triggering reactivity towards formic acid, to produce [dppmAg2(O2CH)]+ and H2. Decarboxylation of [dppmAg2(O2CH)]+ via CID regenerates [dppmAg2(H)]+. These gas-phase insights inspired variable temperature NMR studies that show CO2 and H2 production at 70 °C from solutions containing dppm, AgBF4, NaO2CH and HO2CH.

Suggested Citation

  • Athanasios Zavras & George N. Khairallah & Marjan Krstić & Marion Girod & Steven Daly & Rodolphe Antoine & Philippe Maitre & Roger J. Mulder & Stefanie-Ann Alexander & Vlasta Bonačić-Koutecký & Philip, 2016. "Ligand-induced substrate steering and reshaping of [Ag2(H)]+ scaffold for selective CO2 extrusion from formic acid," Nature Communications, Nature, vol. 7(1), pages 1-8, September.
    • Handle: RePEc:nat:natcom:v:7:y:2016:i:1:d:10.1038_ncomms11746
    DOI: 10.1038/ncomms11746
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