A Nonheme Mononuclear {FeNO}⁷ Complex that Produces N₂ O in the Absence of an Exogenous Reductant.

ABSTRACT: A new nonheme iron(II) complex, Fe^II (Me₃ TACN)((OSi^Ph2 )₂ O) (1), is reported. Reaction of 1 with NO_(g) gives a stable mononitrosyl complex Fe(NO)(Me₃ TACN)((OSi^Ph2 )₂ O) (2), which was characterized by Mössbauer (δ=0.52 mm s^-1 , |ΔE_Q |=0.80 mm s^-1 ), EPR (S=3/2), resonance Raman (RR) and Fe K-edge X-ray absorption spectroscopies. The data show that 2 is an {FeNO}⁷ complex with an S=3/2 spin ground state. The RR spectrum (λ_exc =458 nm) of 2 combined with isotopic labeling (¹⁵ N, ¹⁸ O) reveals ν(N-O)=1680 cm^-1 , which is highly activated, and is a nearly identical match to that seen for the reactive mononitrosyl intermediate in the nonheme iron enzyme FDPnor (ν(NO)=1681 cm^-1 ). Complex 2 reacts rapidly with H₂ O in THF to produce the N-N coupled product N₂ O, providing the first example of a mononuclear nonheme iron complex that is capable of converting NO to N₂ O in the absence of an exogenous reductant.

SUBMITTER: Dey A 

PROVIDER: S-EPMC8657876 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature