A new nonheme iron(II) complex, FeII(Me3TACN)((OSiPh2)2O) (
A new nonheme iron(II) complex, FeII(Me3TACN)((OSiPh2)2O) (
- Award ID(s):
- 1955527
- PAR ID:
- 10307937
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 60
- Issue:
- 39
- ISSN:
- 1433-7851
- Format(s):
- Medium: X Size: p. 21558-21564
- Size(s):
- p. 21558-21564
- Sponsoring Org:
- National Science Foundation
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Abstract 1 ), is reported. Reaction of1 with NO(g)gives a stable mononitrosyl complex Fe(NO)(Me3TACN)((OSiPh2)2O) (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 that2 is an {FeNO}7complex with anS =3/2 spin ground state. The RR spectrum (λ exc=458 nm) of2 combined with isotopic labeling (15N,18O) 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). Complex2 reacts rapidly with H2O in THF to produce the N‐N coupled product N2O, providing the first example of a mononuclear nonheme iron complex that is capable of converting NO to N2O in the absence of an exogenous reductant. -
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Abstract S/N crosstalk species derived from the interconnected reactivity of H2S and NO facilitate the transport of reactive sulfur and nitrogen species in signaling, transport, and regulatory processes. We report here that simple Fe2+ions, such as those that are bioavailable in the labile iron pool (LIP), react with thionitrite (SNO−) and perthionitrite (SSNO−) to yield the dinitrosyl iron complex [Fe(NO)2(S5)]−. In the reaction of FeCl2with SNO−we were able to isolate the unstable intermediate hydrosulfido mononitrosyl iron complex [FeCl2(NO)(SH)]−, which was characterized by X‐ray crystallography. We also show that [Fe(NO)2(S5)]−is a simple synthon for nitrosylated Fe−S clusters via its reduction with PPh3to yield Roussin's Red Salt ([Fe2S2(NO)4]2−), which highlights the role of S/N crosstalk species in the assembly of fundamental Fe−S motifs.
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Abstract S/N crosstalk species derived from the interconnected reactivity of H2S and NO facilitate the transport of reactive sulfur and nitrogen species in signaling, transport, and regulatory processes. We report here that simple Fe2+ions, such as those that are bioavailable in the labile iron pool (LIP), react with thionitrite (SNO−) and perthionitrite (SSNO−) to yield the dinitrosyl iron complex [Fe(NO)2(S5)]−. In the reaction of FeCl2with SNO−we were able to isolate the unstable intermediate hydrosulfido mononitrosyl iron complex [FeCl2(NO)(SH)]−, which was characterized by X‐ray crystallography. We also show that [Fe(NO)2(S5)]−is a simple synthon for nitrosylated Fe−S clusters via its reduction with PPh3to yield Roussin's Red Salt ([Fe2S2(NO)4]2−), which highlights the role of S/N crosstalk species in the assembly of fundamental Fe−S motifs.
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1 ). A combination of FTIR, solid‐state NMR spectroscopy, and reactions with CO or vinyl chloride establish that1 shows similar reactivity patterns as (N^N)Pd(CH3)Cl activated with Na[B(ArF)4]. Multinuclear13C{27Al} RESPDOR and1H{19F} S‐REDOR experiments are consistent with a weakly coordinated ion‐pair between (N^N)Pd−CH3+and [(RFO)3Al−OSi≡)].1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd−CH3]+in solution and incorporates up to 0.4 % methyl acrylate in copolymerization reactions.1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate. -
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Abstract The silylium‐like surface species [iPr3Si][(RFO)3Al−OSi≡)] activates (N^N)Pd(CH3)Cl (N^N=Ar−N=CMeMeC=N−Ar, Ar=2,6‐bis(diphenylmethyl)‐4‐methylbenzene) by chloride ion abstraction to form [(N^N)Pd−CH3][(RFO)3Al−OSi≡)] (
1 ). A combination of FTIR, solid‐state NMR spectroscopy, and reactions with CO or vinyl chloride establish that1 shows similar reactivity patterns as (N^N)Pd(CH3)Cl activated with Na[B(ArF)4]. Multinuclear13C{27Al} RESPDOR and1H{19F} S‐REDOR experiments are consistent with a weakly coordinated ion‐pair between (N^N)Pd−CH3+and [(RFO)3Al−OSi≡)].1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd−CH3]+in solution and incorporates up to 0.4 % methyl acrylate in copolymerization reactions.1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate.
