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{FeNO}7 -Type Halogenido Nitrosyl Ferrates: Syntheses, Bonding, and Photoinduced Linkage Isomerism
Areenan In-Iam1, Markus Wolf1, Claudia Wilfer1
1Department of Chemistry, Ludwig-Maximilians-Universitaet, Butenandtstrasse 5-13, Haus D, München, 81377, Germany.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|October 23, 2018
Summary
Mononitrosyl-iron compounds ({FeNO}7) with quartet spin states were studied. Researchers developed clean preparation methods and determined structural parameters for key iron-nitrosyl species, including the [FeCl3(NO)]- ion.
Area of Science:
- Inorganic Chemistry
- Bioinorganic Chemistry
- Coordination Chemistry
Background:
- Mononitrosyl-iron compounds ({FeNO}7) exist as doublet (S=1/2) and quartet (S=3/2) spin variants.
- Quartet spin states are stabilized by weak-field co-ligands, with aqua-only ligation observed in [Fe(H2O)5(NO)]2+.
- The chloride variant, [FeCl3(NO)]-, is a prototype for biologically significant sulfur-bonded {FeNO}7 (S=3/2) species.
Purpose of the Study:
- To establish clean preparative routes for [FeCl3(NO)]- and related dinitrosyliron species ([FeCl2(NO)2]-).
- To determine reliable structural parameters for these historically significant but poorly characterized iron-nitrosyl complexes.
- To investigate the ground- and excited-state properties and photoinduced isomers of these compounds.
Main Methods:
- Synthesis and characterization of iron-nitrosyl complexes.
- X-ray crystallography for structural determination.
- Computational studies (DFT) for electronic structure and excited states.
- Spectroscopic analysis to characterize photoinduced isomers.
Main Results:
- Clean preparative methods were developed for [FeCl3(NO)]- and [FeCl2(NO)2]-.
- Accurate structural parameters were obtained for these species.
- Computational analysis provided insights into chromophoric transitions and ground-state properties.
- A single photoinduced linkage isomer of the paramagnetic nitrosyl-metal coordination entity was confirmed.
Conclusions:
- This work resolves long-standing issues in the preparation and structural characterization of key {FeNO}7 and dinitrosyliron species.
- The findings provide a foundation for understanding the electronic and photophysical properties of these biologically relevant compounds.
- The identification of a photoinduced linkage isomer opens new avenues for exploring their reactivity and potential applications.
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