A Highly Active N‐Heterocyclic Carbene Manganese(I) Complex for Selective Electrocatalytic CO2 Reduction to CO. Issue 17 (14th March 2018)

• Record Type: Journal Article
• Authors: Franco, Federico; Pinto, Mara F.; Royo, Beatriz; Lloret‐Fillol, Julio
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 17(2018)
• Page Start: 4603
• Page End: 4606
• Publication Date: 2018-03-14
• Subjects: carbon dioxide -- electrocatalysis -- manganese -- N-heterocyclic carbenes -- spectroelectrochemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201800705
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: We report here the first purely organometallic fac ‐[Mn I (CO)3 (bis‐ Me NHC)Br] complex with unprecedented activity for the selective electrocatalytic reduction of CO2 to CO, exceeding 100 turnovers with excellent faradaic yields ( η CO ≈95 %) in anhydrous CH3 CN. Under the same conditions, a maximum turnover frequency (TOFmax ) of 2100 s −1 was measured by cyclic voltammetry, which clearly exceeds the values reported for other manganese‐based catalysts. Moreover, the addition of water leads to the highest TOFmax value (ca. 320 000 s −1 ) ever reported for a manganese‐based catalyst. A Mn I tetracarbonyl intermediate was detected under catalytic conditions for the first time. Abstract : The organometallic complex fac ‐[Mn I (CO)3 (bis‐ Me NHC)Br] is a very active catalyst for the selective electrocatalytic reduction of CO2 to CO, exceeding 100 turnovers with excellent faradaic yields ( η CO ≈95 %) in anhydrous CH3 CN. The addition of water leads to the highest maximum turnover frequency (TOFmax ≈ 320 000 s −1 ) ever reported for a manganese‐based catalyst.