Computational study of relevant factors during catalytic methane oxidation by biomimetic Cu model complexes + Computational study of relevant factors during metal-catalyzed carbonylations of alkanes

The work proposed in the first project aims at identifying important structural, electronic and environmental features of synthetic Cu complexes for their ability to catalytically oxidize methane to methanol with O2 and possibly other cosubstrates. To this end, a series of model complexes will be generated and studied in silico by means of state-of-the-art electronic structure methods. With accurate predictions about reaction energies and barriers for each model complex at hand, the limiting factors will be determined and put in a chemical context. For example, cooperativity between the Cu center and its ligand environment but also with solvent molecules to stabilize reaction intermediates and/or transition state will be the target of our investigation. Finally, we hope to establish design guidelines based on the obtained that can be utilized to achieve an enhanced catalytic activity.
The second project aims at gaining insight into the chemical and physical properties of different bifunctional systems that (supposedly) achieve catalytic carbonylation of alkanes, a highly desirable yet challenging goal. A series of quantum chemical calculations will target three different sets of binuclear transition metal complexes, two of which are part of parallel research efforts in the groups of Prof. Limberg and Prof. Ray. For these systems, our results will help to interpret spectroscopic data and provide information about the reaction mechanism that underlies the observed reactivity. In addition, a study of a yet fictitious combination of Ir pincer complexes and Fe or Co carbonyl complexes will scrutinize the performance of this combination and furthermore highlight the influence of the geometrical arrangement of two active units in bifunctional systems in the present context.