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The Fe 2 (NO) 2 Diamond Core: A Unique Structural Motif In Non‐Heme Iron–NO Chemistry
- Source :
- Angewandte Chemie International Edition. 58:17695-17699
- Publication Year :
- 2019
- Publisher :
- Wiley, 2019.
-
Abstract
- Non-heme high-spin (hs) {FeNO}8 complexes have been proposed as important intermediates towards N2 O formation in flavodiiron NO reductases (FNORs). Many hs-{FeNO}8 complexes disproportionate by forming dinitrosyl iron complexes (DNICs), but the mechanism of this reaction is not understood. While investigating this process, we isolated a new type of non-heme iron nitrosyl complex that is stabilized by an unexpected spin-state change. Upon reduction of the hs-{FeNO}7 complex, [Fe(TPA)(NO)(OTf)](OTf) (1), the N-O stretching band vanishes, but no sign of DNIC or N2 O formation is observed. Instead, the dimer, [Fe2 (TPA)2 (NO)2 ](OTf)2 (2) could be isolated and structurally characterized. We propose that 2 is formed from dimerization of the hs-{FeNO}8 intermediate, followed by a spin state change of the iron centers to low-spin (ls), and speculate that 2 models intermediates in hs-{FeNO}8 complexes that precede the disproportionation reaction.
- Subjects :
- Spin states
010405 organic chemistry
Dimer
Diamond
Disproportionation
Bioinorganic chemistry
General Medicine
General Chemistry
engineering.material
Type (model theory)
010402 general chemistry
01 natural sciences
Catalysis
0104 chemical sciences
chemistry.chemical_compound
Crystallography
chemistry
engineering
Non heme iron
Structural motif
Subjects
Details
- ISSN :
- 15213773 and 14337851
- Volume :
- 58
- Database :
- OpenAIRE
- Journal :
- Angewandte Chemie International Edition
- Accession number :
- edsair.doi.dedup.....b5560c5d10836d6fea99947643aaa87b