Journal article

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

Athanasios Zavras, George N Khairallah, Marjan Krstic, Marion Girod, Steven Daly, Rodolphe Antoine, Philippe Maitre, Roger J Mulder, Stefanie-Ann Alexander, Vlasta Bonacic-Koutecky, Philippe Dugourd, Richard AJ O'Hair

NATURE COMMUNICATIONS | NATURE PUBLISHING GROUP | Published : 2016

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 Lew..

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Grants

Awarded by ARC


Awarded by European Research Council under the European Union


Awarded by French FT-ICR network


Funding Acknowledgements

We thank the ARC for financial support via grant DP150101388 (to R.A.J.O. and P.D.). A.Z. acknowledges the award of an Australian Postgraduate PhD Scholarship. The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (FP7/2007-2013 Grant Agreement No. 320659). Financial support from the French FT-ICR network (FR 3624 CNRS) for conducting the research is gratefully acknowledged. V.B.-K. and M.K. acknowledge Prof. Miroslav Radman at MedILS and Split-Dalmatia County for kind support.