Palladium-catalyzed liquid-phase hydrogenation/hydrogenolysis of disulfides

Ekaterina K. Novakova, Leanne McLaughlin, Robbie Burch, Paul Crawford, Ken Griffin, Christopher Hardacre*, Peijun Hu, David W. Rooney

*Corresponding author for this work

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

For the first time, the hydrogenation/hydrogenolysis of a range of disulfides has been achieved over a supported palladium catalyst using hydrogen under relatively benign conditions. These unexpected results demonstrate that it is possible to avoid the poisoning of the catalyst by either the nitrogen-containing groups or the sulfur species, allowing both efficient reaction and recycling of the catalyst under the proper conditions (e.g., at low temperatures). A slight loss in activity was found on recycling; however, the catalyst activity can be recovered using hydrogen pretreatment. The reaction mechanism for the hydrogenolysis and hydrogenation of ortho-, meta-, and para-dinitrodiphenyldisulfide to the corresponding aminothiophenol has been elucidated. Density functional theory calculations were used to investigate the adsorption mode of the dinitrodiphenyldisulfides; a clear dependence on adsorption geometry was found regarding whether the molecule is cleaved at the S-S bond before the reduction of the nitro group or vice versa. This study demonstrates the versatility of these catalysts for the hydrogenation/hydrogenolysis of sulfur-containing molecules, which normally are considered poisons, and will extend their use to a new family of substrates. (C) 2007 Elsevier Inc. All rights reserved.

Original languageEnglish
Pages (from-to)93-101
Number of pages9
JournalJournal of Catalysis
Volume249
Issue number1
DOIs
Publication statusPublished - 01 Jul 2007

Keywords

  • PLATINUM
  • REGENERATION
  • palladium
  • PD/AL2O3
  • ALUMINA CATALYST
  • hydrogenolysis
  • amine
  • SELECTIVE REDUCTION
  • hydrogenation
  • HYDROGENATION
  • PD
  • ADSORPTION
  • SULFUR TOLERANCE
  • catalyst
  • sulfide
  • heterogeneous
  • nitro
  • NUCLEOPHILIC CLEAVAGE

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