The Fe2 (NO)2 Diamond Core: A Unique Structural Motif In Non-Heme Iron-NO Chemistry.
Angew Chem Int Ed Engl
; 58(49): 17695-17699, 2019 12 02.
Article
em En
| MEDLINE
| ID: mdl-31550416
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.
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Texto completo:
1
Coleções:
01-internacional
Temas:
Agentes_cancerigenos
Base de dados:
MEDLINE
Assunto principal:
Ferro
/
Óxido Nítrico
/
Óxidos de Nitrogênio
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Ano de publicação:
2019
Tipo de documento:
Article
País de afiliação:
Estados Unidos