Revealing the Mechanistic Features of an Electrosynthetic Catalytic Reaction and the Role of Redox Mediators through DFT Calculations and Microkinetic Modeling

Identifier:  imarina:9374777

Handle: https://hdl.handle.net/20.500.11797/imarina9374777

Authors:  Díaz-Ruiz, M; Nieto-Rodríguez, M; Maseras, F

Abstract:
Organic electrosynthesis is an emerging field that provides original selectivity while adding features of atom economy, sustainability, and selectivity. Electrosynthesis is often enhanced by redox mediators or electroauxiliaries. The mechanistic understanding of organic electrosynthesis is however often limited by the low lifetime of intermediates and its difficult detection. In this work, we report a computational analysis of the mechanism of an appealing reaction previously reported by Mei and co-workers which is catalyzed by copper and employs iodide as redox mediator. Our scheme combines DFT calculations with microkinetic modeling and covers both the reaction in solution and the electrodic steps. A detailed mechanistic scheme is obtained which reproduces well experimental data and opens perspectives for the general treatment of these processes. Electrosynthetic catalysis through calculation. A computational study with density functional theory and microkinetic modeling is able to characterize all the steps in the catalytic cycle of a representative copper-catalyzed C-H amination. image