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• W2909905237 endingPage "1413" @default.
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• W2909905237 abstract "Fungal denitrification plays a crucial role in the nitrogen cycle and contributes to the total N2O emission from agricultural soils. Here, cytochrome P450 NO reductase (P450nor) reduces two NO to N2O using a single heme site. Despite much research, the exact nature of the critical “Intermediate I” responsible for the key N–N coupling step in P450nor is unknown. This species likely corresponds to a Fe-NHOH-type intermediate with an unknown electronic structure. Here we report a new strategy to generate a model system for this intermediate, starting from the iron(III) methylhydroxylamide complex [Fe(3,5-Me-BAFP)(NHOMe)] (1), which was fully characterized by 1H NMR, UV–vis, electron paramagnetic resonance, and vibrational spectroscopy (rRaman and NRVS). Our data show that 1 is a high-spin ferric complex with an N-bound hydroxylamide ligand that is strongly coordinated (Fe–N distance, 1.918 Å; Fe-NHOMe stretch, 558 cm–1). Simple one-electron oxidation of 1 at −80 °C then cleanly generates the first model system for Intermediate I, [Fe(3,5-Me-BAFP)(NHOMe)]+ (1+). UV–vis, resonance Raman, and Mössbauer spectroscopies, in comparison to the chloro analogue [Fe(3,5-Me-BAFP)(Cl)]+, demonstrate that 1+ is best described as an FeIII-(NHOMe)• complex with a bound NHOMe radical. Further reactivity studies show that 1+ is highly reactive toward NO, a reaction that likely proceeds via N–N bond formation, following a radical–radical-type coupling mechanism. Our results therefore provide experimental evidence, for the first time, that an FeIII-(NHOMe)• electronic structure is indeed a reasonable electronic description for Intermediate I and that this electronic structure is advantageous for P450nor catalysis because it can greatly facilitate N–N bond formation and, ultimately, N2O generation." @default.
• W2909905237 created "2019-01-25" @default.
• W2909905237 creator A5011061327 @default.
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• W2909905237 date "2019-01-09" @default.
• W2909905237 modified "2023-10-17" @default.
• W2909905237 title "Synthetic Model Complex of the Key Intermediate in Cytochrome P450 Nitric Oxide Reductase" @default.
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• W2909905237 doi "https://doi.org/10.1021/acs.inorgchem.8b02947" @default.
• W2909905237 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/30623648" @default.
• W2909905237 hasPublicationYear "2019" @default.
• W2909905237 type Work @default.
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