“Mechanism of hydrogenation and transfer hydrogenation of polar unsaturations catalyzed by non N-H systems”
Horizon2020, Marie Curie action “IIF”, Contract No. 654198 (2015-2017)
Starting date: July 12, 2014
End date: July 11, 2017
Experienced Research hired: Dr. S. M. Wahidur Rahaman (Ph.D. 2015 IIT Kanpur, India)
Host Institution: Laboratory of Coordination Chemistry, CNRS (UPR 8241), Toulouse, France
Host supervisor: Prof. Rinaldo Poli
The project addresses the reduction of compounds containing polar unsaturations, catalyzed by metal complexes under strongly basic conditions. This is an important reaction that enters the manufacture of many high added value fine chemicals. The role of the strong base for catalysts that do not contain active protons in the ligand donor functions is unclear, as well as the relationship between the mechanisms of hydrogenation by H2 and transfer hydrogenation, for instance by alcohols or formic acid. The sought mechanistic understanding can lead to the design of improved catalysts and operating conditions. The project is being implemented by a multifaceted approach that includes synthesis, characterization, catalysis, kinetics, and computations and is further enriched by parahydrogen NMR studies through a 3-month secondment at the University of York. This multisectorial training puts the ER on an excellent basis to further develop his professional career in research. The ER has an excellent basic training from one of the premier institutions in his Country and an outstanding publication record. The ER is also depeloping transferrable skills by assisting the permanent staff with mentoring undergraduate students in the group. He has delivered presentations at internal group meetings and oral/poster presentations at two international conferences. he has also contributed to drafting his research publications.
E. M. Titova, S. M. W. Rahaman, E. S. Shubina, R. Poli, N. V. Belkova*, E. Manoury*
“Catalytic redox isomerization of allylic alcohols with rhodium and iridium complexes with ferrocene phosphine-thioether ligands”
J. Mol. Catal. A 2017, 426, 376-380.
DOI: 10.1016/j.molcata.2016.08.014
Raw data available at: hal-01496934
S. M. W. Rahaman, J.-C. Daran, E. Manoury, R. Poli*
“The cyclooctadiene ligand in [IrCl(COD)]2 is hydrogenated under transfer hydrogenation conditions: a study in the presence of PPh3 and a strong base in isopropanol”
J. Organometal. Chem., 2017, 829, 14-21. (Frontiers in Organometallic Chemistry” special issue
DOI: 10.1016/j.jorganchem.2016.10.009
Raw data available at: hal-01455813
3rd European Colloquium on Inorganic Reaction Mechanisms (ECIRM), Krakow, Poland, June 21-25, 2016.
S. M. W. Rahaman, E. Manoury, R. Poli
“Rhodium and Iridium-catalyzed Allylic Alcohol Isimerization/Hydrogenation”
(poster presentation)
Organometallic and Coordination Chemistry: Achievements and Challenges (VI Razuvaev Lectures)
Volga river, Nizhny Novgorod - Kazan - Samara - Cheboksary - Nizhny Novgorod, September 18-23, 2015
S. M. W. Rahaman, A. Sinha, S. Dinda, T. Ghatak, J. K. Bera
"C-H Bond Activation at the iridium Center"
(oral presentation)
8 June 2017
"Progress report on the IrI(η4-diene-catalyzed ketone hydrogenation"
2 June 2016
"On the Mechanism of IrI(η4-diene) Precatalyst Activation by Strong Bases in Isopropanol"
10 September 2015
"C-H Bond Activation at the Iridium Center"
Host institution: University of York
Secondment period: 1 September 2016 - 30 November 2016.
Secondment mentor: Prof. Simon B. Duckett
Activity: Para-hydrogen 1H NMR studies of the H2 addition to [Ir(COD)(PS)]+
3rd European Colloquium on Inorganic Reaction Mechanisms (ECIRM), Krakow, Poland, June 21-25, 2016.
S. M. W. Rahaman, E. Deydier, E. Manoury, A. Lledós, R. Poli
“A new paradigm for outer sphere hydrogenation with non deprotonatable ligands”
(contributed oral presentation)
Organometallic and Coordination Chemistry: Achievements and Challenges (VI Razuvaev Lectures)
Volga river, Nizhny Novgorod - Kazan - Samara - Cheboksary - Nizhny Novgorod, September 18-23, 2015
R. Poli, J. M. Hayes, E. Deydier, G. Ujaque, A. Lledós, R. Malacea and E. Manoury:
“A new paradigm for outer sphere hydrogenation with non deprotonatable ligands”
(invited oral presentation)