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The Fe2 (NO)2 Diamond Core: A Unique Structural Motif In Non-Heme Iron-NO Chemistry.

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.

SUBMITTER: Dong HT 

PROVIDER: S-EPMC6878145 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature

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The Fe<sub>2</sub> (NO)<sub>2</sub> Diamond Core: A Unique Structural Motif In Non-Heme Iron-NO Chemistry.

Dong Hai T HT   Speelman Amy L AL   Kozemchak Claire E CE   Sil Debangsu D   Krebs Carsten C   Lehnert Nicolai N  

Angewandte Chemie (International ed. in English) 20191023 49

Non-heme high-spin (hs) {FeNO}<sup>8</sup> complexes have been proposed as important intermediates towards N<sub>2</sub> O formation in flavodiiron NO reductases (FNORs). Many hs-{FeNO}<sup>8</sup> 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-{FeN  ...[more]

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