In:
Angewandte Chemie, Wiley, Vol. 133, No. 39 ( 2021-09-20), p. 21728-21734
Abstract:
A new nonheme iron(II) complex, Fe II (Me 3 TACN)((OSi Ph2 ) 2 O) ( 1 ), is reported. Reaction of 1 with NO (g) gives a stable mononitrosyl complex Fe(NO)(Me 3 TACN)((OSi Ph2 ) 2 O) ( 2 ), which was characterized by Mössbauer ( δ =0.52 mm s −1 , |Δ E 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 H 2 O in THF to produce the N‐N coupled product N 2 O, providing the first example of a mononuclear nonheme iron complex that is capable of converting NO to N 2 O in the absence of an exogenous reductant.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v133.39
DOI:
10.1002/ange.202109062
Language:
English
Publisher:
Wiley
Publication Date:
2021
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