A Non‐Macrocycle Thiolate‐Based Cobalt Catalyst for Selective O2 Reduction into H2O

• DOI: 10.1002/cctc.202400270
• Publication Date: 2024-04-03T08:29:10Z
• Authors: Lili Sun; Javier Gutierrez; Alan Le Goff; David Gatineau; Timothy A. Jackson; Marcello Gennari; Carole Duboc
• Keywords: dioxygen reduction; redox chemistry; cobalt complex; electrocatalysis; thiolate ligand; [CHIM.COOR]Chemical Sciences/Coordination chemistry; inorganic chemistry; [CHIM.CATA]Chemical Sciences/Catalysis; 540; homogeneous catalysis

Abstract The reduction of dioxygen to produce selectively H 2 O or is crucial in various fields. While platinum‐based materials excel 4H + /4e − oxygen reaction (ORR) catalysis, cost and resource limitations drive the search for cost‐effective abundant transition metal catalysts. It thus great importance understand how selectivity efficiency 3d‐metal ORR catalysts can be tuned. In this context, we report on a Co complex supported by bisthiolate N2S2‐donor ligand acting as homogeneous catalyst acetonitrile solutions both presence one‐electron reducing agent (selectivity 93 % TOFi=3 000 h −1 ) under electrochemically‐assisted conditions (0.81 V <η<1.10 V, between 85 95 %). Interestingly, such predominant pathway Co‐based rare, highlighting key role thiolate donor ligand. Besides, chemical inverse with respect Mn Fe same ligand, which evidences impact nature ion selectivity.