Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 49, Pages 17695-17699Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201911968
Keywords
dinitrosyl iron complexes (DNICs); model complexes; nitric oxide; non-heme iron complexes
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Funding
- National Science Foundation [CHE-1608331]
- National Institutes of Health [GM-127079]
- NSF-GRFP fellowship
- NSF-Rackham predoctoral fellowship
- NSF [CHE-0840456]
- Robert W. Parry Scholarship
- Eastman Research Fellowship
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Non-heme high-spin (hs) {FeNO}(8) complexes have been proposed as important intermediates towards N2O 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 N2O formation is observed. Instead, the dimer, [Fe-2(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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