Electrification of a Milstein-type catalyst for alcohol reformation. Issue 44 (3rd November 2022)

• Record Type: Journal Article
• Authors: Tocqueville, Damien; Crisanti, Francesco; Guerrero, Julian; Nubret, Esther; Robert, Marc; Milstein, David; von Wolff, Niklas
• Is Part Of: Chemical science. Volume 13:Issue 44(2022)
• Page Start: 13220
• Page End: 13224
• Publication Date: 2022-11-03
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d2sc04533h
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Electrification of the Milstein catalyst enabled successful molecular electrocatalytic oxidation of ethanol to the four-electron products acetate and ethyl acetate. Abstract : Novel energy and atom efficiency processes will be keys to develop the sustainable chemical industry of the future. Electrification could play an important role, by allowing to fine-tune energy input and using the ideal redox agent: the electron. Here we demonstrate that a commercially available Milstein ruthenium catalyst (1 ) can be used to promote the electrochemical oxidation of ethanol to ethyl acetate and acetate, thus demonstrating the four electron oxidation under preparative conditions. Cyclic voltammetry and DFT-calculations are used to devise a possible catalytic cycle based on a thermal chemical step generating the key hydride intermediate. Successful electrification of Milstein-type catalysts opens a pathway to use alcohols as a renewable feedstock for the generation of esters and other key building blocks in organic chemistry, thus contributing to increase energy efficiency in organic redox chemistry.