Electrokinetic Studies of Epoxidation of Olefins using Fe-bTAML system

Avinash, Sanapala (2021) Electrokinetic Studies of Epoxidation of Olefins using Fe-bTAML system. Masters thesis, Indian Institute of Science Education and Research Kolkata.

Text (MS Dissertation of Sanapala Avinash (16MS021)) 16MS021_Thesis_file.pdf - Submitted Version Restricted to Repository staff only Download (2MB)

Abstract

The selective functionalization of C=C bonds, is one of the most valued upon reaction phenomenon owing to the importance of epoxides in industries as well as for chemists. In nature this reaction is carried out very efficiently and selectively with different enzymes. Research in this area over decades implies that higher oxidized species of iron is a key intermediate in enzymes with iron active centre that catalyze selective oxidation reactions. Reciprocating high valent iron oxo species at room temperature is considered key to addressing the use of stoichiometric amounts of oxidants in C=C bond activation. This procedure is possible by the use of molecular iron catalyst ‘the biuret-modified tetra-amido macrocyclic ligand (FebTAML)’. The oxidation of olefins to form epoxides using electrochemical methods with [(bTAML)FeIII-Cl], as the redox mediator and water as the oxygen source. But studies are yet to be reported about kinetic rates of the Oxygen-atom transfer from FeV(O) species to olefins for the formation of respective epoxides. First-order rate constants (k2) were measured for different olefins with FeV(O) species using Cyclic Voltammetry. Furthermore, a Hammett value of -3.022 was observed in case of electrochemical oxidation of 4-substituted styrene derivatives which suggest the electrophilic character pertaining to iron-oxo species. The mechanistic pathway of the oxygen transfer was also analyzed.

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