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Title: Functional Mononitrosyl Diiron(II) Complex Mediates the Reduction of NO to N 2 O with Relevance for Flavodiiron NO Reductases
PAR ID:
10048550
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  
Publisher / Repository:
American Chemical Society
Date Published:
Journal Name:
Journal of the American Chemical Society
Volume:
139
Issue:
41
ISSN:
0002-7863
Page Range / eLocation ID:
14380 to 14383
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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  1. null (Ed.)
  2. Abstract

    Non‐heme high‐spin (hs) {FeNO}8complexes have been proposed as important intermediates towards N2O formation in flavodiiron NO reductases (FNORs). Many hs‐{FeNO}8complexes 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}7complex, [Fe(TPA)(NO)(OTf)](OTf) (1), the N‐O stretching band vanishes, but no sign of DNIC or N2O formation is observed. Instead, the dimer, [Fe2(TPA)2(NO)2](OTf)2(2) could be isolated and structurally characterized. We propose that2is formed from dimerization of the hs‐{FeNO}8intermediate, followed by a spin state change of the iron centers to low‐spin (ls), and speculate that2models intermediates in hs‐{FeNO}8complexes that precede the disproportionation reaction.

     
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