Formic Acid Dehydrogenation by Ruthenium Catalyst – Computational and Kinetic Analysis with the Energy Span Model

Alexander Frenklah, Ziv Treigerman, Yoel Sasson, Sebastian Kozuch

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

Abstract

The ruthenium (cis-RuCl2(DPPM)2) based catalytic dehydrogenation reaction of formic acid in the presence of an amine base in a biphasic system experimentally tested by Treigerman and Sasson (ChemistrySelect 2017, 2, 5816) was studied computationally to ascertain its mechanism. The energy span model was applied on the double-hybrid DFT computed energy profile to comprehend its kinetics. The catalytic network includes three possible interconnected cycles depending on the ancillary ligands, going through decarboxylation, protonation and H2 release. The dihydride cycle proves to be the most efficient after pre-activation steps coming from the other cycles. The turnover frequency (TOF) determining intermediate (TDI) is the formatohydride species, while the TOF determining transition state (TDTS) corresponds to a formate decarboxylation. Herein we include the effect of reactants concentrations to the energy span model, which proved to be essential to comprehend the experimental ESI-MS results and to propose a more accurate mechanism.

Original languageEnglish
Pages (from-to)591-597
Number of pages7
JournalEuropean Journal of Organic Chemistry
Volume2019
Issue number2
DOIs
StatePublished - 23 Jan 2019

Keywords

  • Density functional calculations
  • Energy span model
  • Formic acid
  • Homogenous catalysis
  • Hydrogen storage

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

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