A Non-Heme Diiron Complex for (Electro)catalytic Reduction of Dioxygen: Tuning the Selectivity through Electron Delivery

Lianke Wang, Marcello Gennari, Fabián G. Cantú Reinhard, Javier Gutiérrez, Adina Morozan, Christian Philouze, Serhiy Demeshko, Vincent Artero, Franc Meyer, Sam P. de Visser, Carole Duboc

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    In the oxygen reduction reaction (ORR) domain, the investigation of new homogeneous catalysts is a crucial step toward the full comprehension of the key structural and/or electronic factors that control catalytic efficiency and selectivity. Herein, we report a unique non-heme diiron complex that can act as a homogeneous ORR catalyst in acetonitrile solution. This iron(II) thiolate dinuclear complex, [FeII2(LS)(LSH)] ([Fe2SH]+) (LS2- = 2,2'-(2,2'-bipyridine-6,6'-diyl)bis(1,1-diphenylethanethiolate)) contains a thiol group in the metal coordination sphere. [Fe2SH]+ is an efficient ORR catalyst both in the presence of a one-electron reducing agent and under electrochemically assisted conditions. However, its selectivity is dependent on the electron delivery pathway; in particular, the process is selective for H2O2 production under chemical conditions (up to ∼95%), whereas H2O is the main product during electrocatalysis (less than ∼10% H2O2). Based on computational work alongside the experimental data, a mechanistic proposal is discussed that rationalizes the selective and tunable reduction of dioxygen.

    Original languageEnglish
    Pages (from-to)8244-8253
    Number of pages10
    JournalJournal of the American Chemical Society
    Issue number20
    Early online date26 Apr 2019
    Publication statusPublished - 22 May 2019

    Research Beacons, Institutes and Platforms

    • Manchester Institute of Biotechnology


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