A Nonheme Mononuclear {FeNO} Complex That Produces N O in the Absence of an Exogenous Reductant
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A new nonheme iron(II) complex, Fe (Me TACN)((OSi ) O) (1), is reported. Reaction of 1 with NO gives a stable mononitrosyl complex Fe(NO)(Me TACN)((OSi ) O) (2), which was characterized by Mössbauer (δ=0.52 mm s , |ΔE |=0.80 mm s ), EPR (S=3/2), resonance Raman (RR) and Fe K-edge X-ray absorption spectroscopies. The data show that 2 is an {FeNO} complex with an S=3/2 spin ground state. The RR spectrum (λ =458 nm) of 2 combined with isotopic labeling ( N, O) reveals ν(N-O)=1680 cm , 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 ). Complex 2 reacts rapidly with H O in THF to produce the N-N coupled product N O, providing the first example of a mononuclear nonheme iron complex that is capable of converting NO to N O in the absence of an exogenous reductant.
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