Quantification of Substituent Effects in Catalysis by Combined Experimental and Theoretical Charge Density Studies: The Key for Efficient Ligand Tailoring in Catalysis

• Antragsteller: Professor Dr. Werner R. Thiel
• Fachliche Zuordnung: Analytische Chemie
• Förderung: Förderung von 2005 bis 2008
• Projektkennung: Deutsche Forschungsgemeinschaft (DFG) - Projektnummer 5450323

• Erstellungsjahr: 2007

Zusammenfassung der Projektergebnisse

Topological analysis of experimental and theoretical charge densities of several molybdenum bisperoxo benchmarks revealed several criteria which influence/characterize the electronic structure of these catalysts and might allow us to optimize their performance in epoxidation reactions: (i) the different orientation of the oxygen lone pairs in mono vs. bisperoxo complexes might hinder/favour the coordination of the oxidation reactants (organic peroxides) via hydrogen bonding; (ii) electron withdrawing substituents in the pyrazolyl rings apparently trigger not only the A:B isomer ratio but also the ease of the Mo-Npz bond dissociation – which initiates the coordination of the oxidation reactant (organic peroxides).