TY - JOUR
T1 - Formic Acid Dehydrogenation by Ruthenium Catalyst – Computational and Kinetic Analysis with the Energy Span Model
AU - Frenklah, Alexander
AU - Treigerman, Ziv
AU - Sasson, Yoel
AU - Kozuch, Sebastian
N1 - Publisher Copyright:
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/1/23
Y1 - 2019/1/23
N2 - 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.
AB - 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.
KW - Density functional calculations
KW - Energy span model
KW - Formic acid
KW - Homogenous catalysis
KW - Hydrogen storage
UR - http://www.scopus.com/inward/record.url?scp=85059619222&partnerID=8YFLogxK
U2 - 10.1002/ejoc.201801226
DO - 10.1002/ejoc.201801226
M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???
AN - SCOPUS:85059619222
SN - 1434-193X
VL - 2019
SP - 591
EP - 597
JO - European Journal of Organic Chemistry
JF - European Journal of Organic Chemistry
IS - 2
ER -
