High-valent Fe(IV)-oxo species have been found to be key oxidizing intermediates in the mechanisms of mononuclear iron heme and non-heme enzymes. [1] Synthetic non-heme Fe(IV)-oxo molecular complexes have been successfully synthesized and characterized, but their catalytic reactivity is typically lower than the enzymatic analogues. One of the reasons of their lower reactivity is the self-oxidation mechanism that undergo due to the close proximity of ligand's methyl groups to the active site. We have performed wave function theory calculations in a series of non-heme Fe(IV)-oxo model complexes in order to elucidate the electronic properties and the ligand field effects on the substrate oxidation and self-oxidation reactions. Such properties can be used as descriptors of catalytic activity. [2] Currently, we are examining a variety of known structure-function relations in order to develop predictive machine learning models for the examination of a large database of Fe(IV)-oxo complexes. Our novel methodology is based on the encoding of geometrical and electronic structural information with persistent homology and aims to the automated search of a large fraction of the chemical space for in silico catalyst optimization. [3] Finally, other challenging reaction mechanisms studied by our research group (P-C coupling, hydrogenation of olefins promoted by metal-organic frameworks) will be discussed.
[1] M. Guo, T. Corona, K. Ray, W. Nam ACS Cent. Sci., 2019, 5, 13-28.
[2] J. K. Kirkland, S. N. Khan, B. Casale, E. Miliordos, K.D. Vogiatzis Phys. Chem. Chem. Phys., 2018, 20, 28786-28795.
[3] K. D. Vogiatzis, M. V. Polynski, J. K. Kirkland, J. Townsend, A. Hashemi, C. Liu, E. A. Pidko Chem. Rev. 2019, 119, 2453-2523.
Ομιλητής: Κωνσταντίνος Δ. Βογιατζής
Επίκ. Καθηγητής, Department of Chemistry, University of Tennessee, Knoxville, TN, USA
Ώρα: Παρασκευή, 24 Μαΐου 2019, 15:00