Synthesis and Characterization of Stable Iron Pentacarbonyl Radical Cation Salts. (7th June 2022)

• Record Type: Journal Article
• Authors: Rall, Jan M.; Schorpp, Marcel; Keilwerth, Martin; Mayländer, Maximilian; Friedmann, Christian; Daub, Michael; Richert, Sabine; Meyer, Karsten; Krossing, Ingo
• Is Part Of: Angewandte Chemie. Volume 134:Number 32(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-06-07
• Subjects: Carbonyl Ligands -- Iron -- Radical Ions -- Weakly Coordinating Anions; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202204080
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The open‐shell iron pentacarbonyl cation [Fe(CO)5 ] .+ was isolated by deelectronation, i.e., the single‐electron oxidation of the parent neutral Fe(CO)5 using [phenazine F ] .+ as the [Al(OR F )4 ] − and [F‐{Al(OR F )3 }2 ] − salt (R F =C(CF3 )3 ; phenazine F =perfluoro‐5, 10‐bis(perfluorophenyl)‐5, 10‐dihydrophenazine). [Fe(CO)5 ] .+ [Al(OR F )4 ] − was fully characterized (scXRD analysis, IR, NMR, EPR, 57 Fe spectroscopy, CV and SQUID magnetization study) and, apart from being a compound of fundamental interest, may serve as a precursor for low‐valent iron coordination chemistry. Abstract : The open‐shell iron pentacarbonyl cation [Fe(CO)5 ] .+ was synthesized and isolated as a stable salt for the first time. The strategy involved the use of a strong deelectronator, i.e., single‐electron oxidant, in combination with weakly coordinating anions (WCAs). The iron carbonyl complex is a novel example of low‐valent iron and has thus been fully characterized. Isolation was achieved using standard laboratory conditions in combination with fluorinated benzenes as solvents.