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

• Record Type: Journal Article
• Authors: Franco, Federico; Pinto, Mara F.; Royo, Beatriz; Lloret‐Fillol, Julio
• Is Part Of: Angewandte Chemie. Volume 130:Number 17(2018)
• Page Start: 4693
• Page End: 4696
• Publication Date: 2018-03-14
• Subjects: Elektrokatalyse -- Kohlendioxid -- Mangan -- N-heterocyclische Carbene -- Spektroelektrochemie; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201800705
• Languages: English
• ISSNs: 0044-8249

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 : Der metallorganische Komplex fac ‐[Mn I (CO)3 (bis‐ Me NHC)Br] ist ein hoch aktiver Katalysator der selektiven elektrokatalytischen Reduktion von CO2 zu CO, mit Wechselzahlen über 100 und exzellenten faradayschen Ausbeuten ( η CO ≈95 %) in wasserfreiem CH3 CN. Die Hinzugabe von Wasser führt zur höchsten maximalen Wechselfrequenz (TOFmax ≈320 000 s −1 ), die je für einen Mn‐Katalysator gemessen wurde.