Ligand-induced substrate steering and reshaping of [Ag-2(H)](+) scaffold for selective CO2 extrusion from formic acid

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. [Ag-2(H)](+) and [Ph3PAg2(H)](+) react with formic acid yielding Lewis adducts, while [(Ph3P)(2)Ag-2(H)](+) is unreactive. Using bis(diphenylphosphino) methane (dppm) reshapes the geometry of the binuclear Ag-2(H)(+) scaffold, triggering reactivity towards formic acid, to produce [dppmAg(2)(O2CH)](+) and H-2. Decarboxylation of [dppmAg(2)(O2CH)](+) via CID regenerates [dppmAg(2)(H)](+). These gas-phase insights inspired variable temperature NMR studies that show CO2 and H-2 production at 70 degrees C from solutions containing dppm, AgBF4, NaO2CH and HO2CH.
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Nature Communications, Nature Publishing Group, 2016, 7, pp. Article Number: 11746 〈10.1038/ncomms11746〉
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https://hal.archives-ouvertes.fr/hal-01356285
Contributeur : Agnès Bussy <>
Soumis le : jeudi 25 août 2016 - 13:37:18
Dernière modification le : jeudi 15 mars 2018 - 10:30:28

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Athanasios Zavras, George N. Khairallah, Marjan Krstić, Marion Girod, Steven Daly, et al.. Ligand-induced substrate steering and reshaping of [Ag-2(H)](+) scaffold for selective CO2 extrusion from formic acid. Nature Communications, Nature Publishing Group, 2016, 7, pp. Article Number: 11746 〈10.1038/ncomms11746〉. 〈hal-01356285〉

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