Ir(III)-PC(sp3)P Bifunctional Catalysts for Production of H2 by Dehydrogenation of Formic Acid: Experimental and Theoretical Study

Shirel Cohen, Veniamin Borin, Igor Schapiro*, Sanaa Musa, Sophie De-Botton, Natalia V. Belkova, Dmitri Gelman

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

49 Scopus citations

Abstract

Reversible storage of hydrogen in the form of stable and relatively harmless chemical substances such as formic acid (FA) is one of the cornerstones of a fossil-fuel-free economy. Recently, Ru(III)-PC(sp3)P (where PC(sp3)P = modular dibenzobarrelene-based pincer ligand possessing a pendant functional group) complex 1 has been reported as a mild and E-selective catalyst in semihydrogenation of alkynes with stoichiometric neat formic acid. Discovery of the additive-free protocol for dehydrogenation of FA launched further studies aiming at the rational design of highly efficient catalysts for this reaction operating under neutral conditions. We now report the results of our investigation on a series of bifunctionl PC(sp3)P complexes equipped with different outer-sphere auxiliaries, that allowed us to identify an amine-functionalized Ir(III)-PC(sp3)P complex 3, as a clean and efficient catalyst for the FA dehydrogenation. The catalyst is suitable for fuel-cell applications demonstrating a TON up to 5 × 105 and TOF up to 2 × 104 h-1 (3.8 × 105 and 1.2 × 104 h-1 with no additives). In addition to the practical value of the catalyst, experimental and computational mechanistic studies provide rationale for the design of improved next-generation catalysts.

Original languageAmerican English
Pages (from-to)8139-8146
Number of pages8
JournalACS Catalysis
Volume7
Issue number12
DOIs
StatePublished - 1 Dec 2017

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

Keywords

  • dehydrogenation
  • formic acid
  • hydrogen
  • ligand-metal cooperation
  • pincer complexes

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