The Silver Lining of Dihydrogen Activation

  • Author: David Smith
  • Published Date: 30 June 2015
  • Source / Publisher: Chemistry – A European Journal/Wiley-VCH
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
thumbnail image: The Silver Lining of Dihydrogen Activation

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Activation of dihydrogen is a key step in catalytic hydrogenation. H2 heterolysis has been achieved using frustrated Lewis pairs and a variety of palladium salts. Silver hydrides are thought to be intermediates in Ag-catalyzed aldehyde hydrogenation reactions and have also been shown to undergo photo-induced H2 release, indicating their potential use as catalysts for H2 release from storage media such as formic acid.


Joseph P. Sadighi and co-workers, Georgia Institute of Technology, Atlanta, GA, USA, show that silver fluorides and alkoxides undergo hydrogenolysis to form hydride-bridged disilver cations (pictured). The disilver cations form from silver alkoxides via loss of free alcohol and from silver fluorides via the generation of bifluoride as a counterion.


Kinetic isotope experiments are consistent with the deprotonation of silver-coordinated dihydrogen as the rate-limiting step. These findings represent a key step in finding new catalysts for H2 generation.


 

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Magazine of Chemistry Europe (16 European Chemical Societies)published by Wiley-VCH