A heterogeneous bio-inspired peroxide shunt for catalytic oxidation of organic molecules. Issue 78 (27th August 2020)

• Record Type: Journal Article
• Authors: Mukherjee, Manjistha; Dey, Abhishek
• Is Part Of: Chemical communications. Volume 56:Issue 78(2020)
• Page Start: 11593
• Page End: 11596
• Publication Date: 2020-08-27
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/d0cc03468a
• Languages: English
• ISSNs: 1359-7345

Abstract

Abstract : Iron porphyrins with three different axial ligands installed atop self-assembled monolayer modified gold electrodes can oxidize C–H bonds and epoxidize alkenes efficiently using H2 O2 via the formation of a high-valent intermediate. Abstract : Heme enzymes are capable of catalytically oxidising organic substrates using peroxide via the formation of a high-valent intermediate. Iron porphyrins with three different axial ligands are created on self-assembled monolayer-modified gold electrodes, which can oxidize C–H bonds and epoxidize alkenes efficiently. The kinetic isotope effects suggest that the hydrogen atom transfer reaction by a highly reactive oxidant is likely to be the rate-determining step. Effect of different axial ligands and different secondary structures of the iron porphyrin confirms that the thiolate axial ligand with a hydrophobic distal pocket is the most efficient for this oxidation chemistry.