Ignacio Funes, PhD student under the supervision of Prof. Feliu Maseras (ICIQ), has defended his PhD Thesis entitled
“Computational Chemistry for Homogeneous Redox Catalysis” (assigned to the Physical and Inorganic Chemistry Department of the Universitat Rovira i Virgili) publicly on September 20th at the ICIQ Auditorium.
The members of the evaluation committee were: Prof. Agustí Lledós Falcó (Universitat Autònoma de Barcelona), Prof. Miguel Monge Oroz (Universidad de la Rioja) and Prof. Franziska Schoenebeck (RWTH Aachen University)
This Doctoral Thesis is focused on the computational study by DFT methodology (Density Functional Theory) of homogeneous redox catalized reactions. The first part describes successfully the mechanism of two different catalytic cycles of oxidative coupling reactions. This study found out the explanation about one of the challenging questions on the field, the key role of the external oxidant. We demonstrated the cooperation between different transition metals is essential to catalyze the reaction efficiently and with good selectivities. Additionally, we explained also the regioselectivity of both reactions, in very good agreement with the experimental results. The second reaction was studied in collaboration with the experimental group of professor Frederic Patureau (University of Kaiserslautern).
On the other hand, the second part of the thesis is focused on the theoretical study of water oxidation reaction catalyzed by first-row transition metal complexes. Firstly, we developed a new family of mononuclear copper complexes in collaboration with the experimental group of professor Antoni Llobet (ICIQ), discovering a new mechanism for the oxygen-oxygen bond formation step, the water nucleophilic attack. single electron transfer (SET-WNA). From this point, we extended the new mechanism to other catalytic systems based on copper and ruthenium, redefining the mechanistic scenario for the homogeneous catalytic version of this reaction.
Therefore, this thesis provides a deep theoretical knowledge abour the homogeneous redox catalysis mechanisms by DFT calculations.