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

摘要: Mononitrosyl-iron compounds (MNICs) of the Enemark-Feltham {FeNO}7 type can be divided into a doublet (S=1/2) and 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 long-known "brown-ring" [Fe(H2 O)5 (NO)]2+ cation, which was prepared originally from ferrous salts NO sulfuric acid. A chloride variant this species, green [FeCl3 (NO)]- ion, first analoguosly by using hydrochloric instead As tetrahedral it is simple prototype sulfur-bonded MNICs biological significance. Although has been investigated for more than century, neither clean preparative routes nor reliable structural parameters were available ion related species [FeCl2 (NO)2 ]- prototypical dinitrosyliron (a "DNIC"). In work, both issues have resolved. addition, we report computational study ground- excited-state properties including an assignment chromophoric transitions. Photoinduced metastable isomers characterised combined experimental approach that resulted confirmation single photoinduced linkage isomer paramagnetic nitrosyl-metal coordination entity.