{FeNO}(7)-Type Halogenido Nitrosyl Ferrates: Syntheses, Bonding, and Photoinduced Linkage Isomerism

In-Iam, Areenan; Wolf, Markus; Wilfer, Claudia; Schaniel, Dominik; Woike, Theo und Kluefers, Peter (2019): {FeNO}(7)-Type Halogenido Nitrosyl Ferrates: Syntheses, Bonding, and Photoinduced Linkage Isomerism. In: Chemistry-A European Journal, Bd. 25, Nr. 5: S. 1304-1325

Abstract

Mononitrosyl-iron compounds (MNICs) of the Enemark-Feltham {FeNO}(7) type can be divided into a doublet (S=1/2) and a quartet (S=3/2) spin variant. The latter relies on weak-field co-ligands such as amine carboxylates. Aqua-only co-ligation appears to exist in the long-known "brown-ring" [Fe(H2O)(5)(NO)](2+) cation, which was prepared originally from ferrous salts and NO in sulfuric acid. A chloride variant of this species, the green [FeCl3(NO)](-) ion, was first prepared analoguosly by using hydrochloric instead of sulfuric acid. As a tetrahedral species, it is the simple prototype of sulfur-bonded {FeNO}(7) (S=3/2) MNICs of biological significance. Although it has been investigated for more than a century, neither clean preparative routes nor reliable structural parameters were available for the [FeCl3(NO)](-) ion and related species such as the [FeCl2(NO)(2)](-) ion, a prototypical dinitrosyliron species (a "DNIC"). In this work, both issues have been resolved. In addition, we report on a computational study on the ground- and excited-state properties including an assignment of the chromophoric transitions. Photoinduced metastable isomers were characterised in a combined experimental and computational approach that resulted in the confirmation of a single photoinduced linkage isomer of the paramagnetic nitrosyl-metal coordination entity.

• Dokumententyp: Zeitschriftenartikel
• Fakultät: Chemie und Pharmazie > Department Chemie
• Themengebiete: 500 Naturwissenschaften und Mathematik > 540 Chemie
• ISSN: 0947-6539
• Sprache: Englisch