Studies Towards Electrochemical C-H Activation using a Molecular Iron Catalyst

Hellan, K. M. (2019) Studies Towards Electrochemical C-H Activation using a Molecular Iron Catalyst. Masters thesis, Indian Institute of Science Education and Research Kolkata.

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Abstract

The selective functionalization of C–H bonds, represent the most important industrial processes for converting hydrocarbons into value added products. Nature performs this selective functionalization very efficiently and selectively with different enzymes. Sustained research over decades revealed that higher oxidized species of iron is the key intermediate for natural Fe-containing enzymes that catalyze selective oxidation reactions. So stabilization of a high valent iron oxo at room temperature is the key to functionalize the C–H bond. This was possible by a molecular iron catalyst ‘the biuret-modified tetra-amido macrocyclic ligand (Fe-bTAML)’. Stabilization of the high valent iron oxo was possible by both chemical and photochemical methods in Fe-bTAML system. Electrocatalysis, another way for stabilizing the high valent iron-oxo, overcomes the limitations posed by chemical and photochemical methods. Further, the limitations posed in electrochemical catalysis of [(bTAML)Fe(III)-OH₂] was solved by site isolating the catalyst. This was achieved by designing a pyrene modified (bTAML) system. Herein, for the first time, we have synthesised pyrene conjugated [(bTAML)Fe(III)-OH₂]. Immobilising the catalyst on to the electrode would potentially reduce the problem of dimerisation of [(bTAML)FeIV(OH₂)]¹⁻ leading to the formation of Fe(IV)-O-Fe(IV).

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