A Molecular Low‐Coordinate [Fe‐S‐Fe] Unit in Three Oxidation States. Issue 20 (5th March 2021)

• Record Type: Journal Article
• Authors: Schneider, Christian; Demeshko, Serhiy; Meyer, Franc; Werncke, C. Gunnar
• Is Part Of: Chemistry. Volume 27:Issue 20(2021)
• Page Start: 6348
• Page End: 6353
• Publication Date: 2021-03-05
• Subjects: 57Fe Mössbauer spectroscopy -- electrochemistry -- iron sulfide complex -- magnetism -- nitrogenase; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202100336
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A [Fe‐S‐Fe] subunit with a single sulfide bridging two low‐coordinate iron ions is the supposed active site of the iron‐molybdenum co‐factor (FeMoco) of nitrogenase. Here we report a dinuclear monosulfido bridged diiron(II) complex with a similar complex geometry that can be oxidized stepwise to diiron(II/III) and diiron(III/III) complexes while retaining the [Fe‐S‐Fe] core. The series of complexes has been characterized crystallographically, and electronic structures have been studied using, inter alia, 57 Fe Mössbauer spectroscopy and SQUID magnetometry. Further, cleavage of the [Fe‐S‐Fe] unit by CS2 is presented. Abstract : A dinuclear monosulfido bridged diiron(II) complex is reported that can be oxidized stepwise to diiron(II/III) and diiron(III/III) complexes while retaining the [Fe‐S‐Fe] core. This unprecedented series of low‐coordinate complexes has been thoroughly characterized using inter alia, 57 Fe Mössbauer spectroscopy and SQUID magnetometry.