What Is the Right Level of Activation of a High-Spin {FeNO}⁷ Complex to Enable Direct N-N Coupling? Mechanistic Insight into Flavodiiron NO Reductases.

ABSTRACT: Flavodiiron nitric oxide reductases (FNORs), found in pathogenic bacteria, are capable of reducing nitric oxide (NO) to nitrous oxide (N₂O) to detoxify NO released by the human immune system. Previously, we reported the first FNOR model system that mediates direct NO reduction (Dong, H. T.; J. Am. Chem. Soc. 2018, 140, 13429-13440), but no intermediate of the reaction could be characterized. Here, we present a new set of model complexes that, depending on the ligand substitution, can either mediate direct NO reduction or stabilize a highly activated high-spin (hs) {FeNO}⁷ complex, the first intermediate of the reaction. The precursors, [{Fe^II(MPA-(RPhO)₂)}₂] (1, R = H and 2, R = ^tBu, Me), were pre

SUBMITTER: Dong HT 

PROVIDER: S-EPMC10279474 | biostudies-literature | 2022 Sep

REPOSITORIES: biostudies-literature