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 language | English |
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Pages (from-to) | 591-597 |
Number of pages | 7 |
Journal | European Journal of Organic Chemistry |
Volume | 2019 |
Issue number | 2 |
DOIs | |
State | Published - 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