Issue 16, 2021

Formate-driven catalysis and mechanism of an iridium–copper complex for selective aerobic oxidation of aromatic olefins in water

Abstract

A hetero-dinuclear IrIII–CuII complex with two adjacent sites was employed as a catalyst for the aerobic oxidation of aromatic olefins driven by formate in water. An IrIII–H intermediate, generated through formate dehydrogenation, was revealed to activate terminal aromatic olefins to afford an Ir-alkyl species, and the process was promoted by a hydrophobic [IrIII–H]-[substrate aromatic ring] interaction in water. The Ir-alkyl species subsequently reacted with dioxygen to yield corresponding methyl ketones and was promoted by the presence of the CuII moiety under acidic conditions. The IrIII–CuII complex exhibited cooperative catalysis in the selective aerobic oxidation of olefins to corresponding methyl ketones, as evidenced by no reactivities observed from the corresponding mononuclear IrIII and CuII complexes, as the individual components of the IrIII–CuII complex. The reaction mechanism afforded by the IrIII–CuII complex in the aerobic oxidation was disclosed by a combination of spectroscopic detection of reaction intermediates, kinetic analysis, and theoretical calculations.

Graphical abstract: Formate-driven catalysis and mechanism of an iridium–copper complex for selective aerobic oxidation of aromatic olefins in water

Supplementary files

Article information

Article type
Edge Article
Submitted
04 Dec 2020
Accepted
15 Mar 2021
First published
16 Mar 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2021,12, 5796-5803

Formate-driven catalysis and mechanism of an iridium–copper complex for selective aerobic oxidation of aromatic olefins in water

Y. Shimoyama, Y. Kitagawa, Y. Ohgomori, Y. Kon and D. Hong, Chem. Sci., 2021, 12, 5796 DOI: 10.1039/D0SC06634F

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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