Iron nitrosyl complex

The nitrosyl iron complex Fe( J-mph) NO shows a spin-state transition between the S = f and S = ground states. The structure of the complex is characterized by ... 

Volodin, A.M., Dubkov, K.A. and Lund, A. (2001) Direct ESR detection of S = 3/2 states for nitrosyl iron complexes in FeZSM-5 zeolites, Chem. Phys. Lett., 333, 41. 

Drapier, j. C., Pellat, C., and Henry, Y. (1991). Generation of EPR-detectable nitrosyl-iron complexes in tumor target cells cocultured with activated macrophages. ]. Biol. Chem. 266, 10162-10167. 

Sodium nitroprusside was first prepared and investigated in the middle of the nineteenth century, and a comprehensive summary of the earlier chemical investigations has been published (17). Up to 1910-1930, the addition reactions of bases to NP were explored, involving the characterization of colored intermediates (e.g., with SH-, SR-, and SO3 ), useful for analytical purposes. The hypotensive action of NP was first demonstrated in 1929, and a considerable research effort has attempted to establish the mode of action of NP and its metabolic fate. Questions still arise on the mechanism of NO release from NP in the biological fluids, and we refer to them below. New accounts dealing with modern structural and reactivity issues associated with the coordination of nitrosyl in NP and other complexes have appeared (18-20). From the bioinorganic and environmental viewpoint, nitrosyl iron complexes have been studied with... 

Influence of several nitrosyl-iron complexes on relaxation rates was assessed to establish a MR imaging technique for nitric oxide (NO). " To induce formation of nitrosyl-ion complexes in a biological tissue, isolated rat liver was perfused with a saline solution of the NO donor sodium nitroprus-side (SNP), and the MR signal intensity was examined thereafter. Nitrosyl-iron complexes exhibit a contrast effect at MR imaging that can be exploited for NO imaging in living animals and patients with conventional MR imaging. 

Lewandowska H, Kalinowska M et al (2011) Nitrosyl iron complexes-synthesis, structure and biology. Dalton Trans 40 8273-8289... 

Vanin AF (1991) Endothelium-derived relaxing factor is a nitrosyl iron complex with thiol ligands. FEBS Lett 289 1-3... 

Sanina NA, Syrtsova LA et al (2007) Reactions of sulfiff-nitrosyl iron complexes of g=2.03 family with hemoglobin (Hb) kinetics of Hb-NO formation in aqueous solutions. Nitric Oxide 16 181-188... 

Vasilieva SV, Moshkovskaya EY et al (2004) Genetic signal transduction by nitrosyl-iron complexes in Escherichia coli. Biochemistry 69 883-889... 

Fichtlscherer B, Mvilsch A (2000) MR imaging of nitrosyl-iron complexes experimental study in Ratsl. Radiology 216 225-231... 

Sanina N, Roudneva T et al (2009) Structure and properties of binuclear nitrosyl iron complex with benzimidazole-2-thiolyl. Dalton Trans 1703-1706... 

D Autreaux B, Homer O, Oddou JL, Jeandey C, Gambarelli S, Berthomieu C, Latour JM, Michaud-Soret I. 2004. Spectroscopic description of the two nitrosyl-iron complexes responsible for fur inhibition by nitric oxide. J Am Chem Soc 126(19) 6005-6016. 

Similarly, the reaction of 3-halo-1-alkenes with tetrabutylammonium tricarbonyl-(nitrosyl)ferrate (TBAFe) gives T -allyl(tricarbonyl)(nitrosyl)iron complexes. Treatment of Y-bromo-a,p-unsaturated esters or amides with potassium tricarbonyl-(nitrosyl)ferrate provides planar chiral T] -allyl(dicarbonyl)(nitrosyl)iron complexes. Enantiopure amides as starting materials lead to a low diastereoselectivity, whereas no diastereoselectivity is observed for the chiral esters. The diastereoisomers of the amide-substituted allyliron complexes can be conveniently separated by column chromatography (Scheme 4-80). ... 

Cationic ri -allyl(tetracarbonyl)iron complexes are powerful electrophiles that react with nucleophiles primarily to T -alkene(tetracarbonyl)iron complexes. Those species are rather labile and decompose during workup to afford substituted alkenes. This methodology has been described for the first time by Pearson using organocadmium nucleophiles. Similarly, Ti -allyl(dicarbonyl)(nitrosyl)iron complexes, despite the lacking positive charge, also smoothly react with various nucleophiles. As... 

Amines react with ri -allyl(dicarbonyl)(nitrosyl)iron complexes to give allyl amines. The reaction rate and the regioselectivity is strongly influenced by the substituents on the allyl ligand (Scheme 4-88). Methoxycarbonyl groups turn out to be especially useful as they accelerate the reaction and also enhance the regioselectivity. Y-Amino-a,(3-unsaturated esters are obtained in high yields by this method. ... 

The reaction can also be carried out stereoselectively employing enantiomerically pure planar chiral ri -allyl(dicarbonyl)(nitrosyl)iron complexes. The required complexes are obtained from TBAFe and allyl bromides bearing a chiral auxiliary adjacent to the allyl complex in the form of chiral ester or amide groups (Scheme 4-80). Amination of enantiomerically pure rj -allyliron complexes proceeds with excellent stereoselectivity (de > 98%). Carbanions as nucleophiles give lower de values of 79-86%. The nucleophiles enter preferably anti to the iron complex unit with excellent regiocontrol in... 

The methodology of nucleophilic addition to ri -allyliron complexes has also been applied for natural product synthesis. Thus, the regioselective and stereoselective addition of an organocopper reagent to a neutral Tl -allyl(dicarbonyl)(nitrosyl)iron complex is the key step in the total synthesis of the Cl-Cl 6 fragment of ionomycin (Scheme 4-90). ... 

Ti -Allyl(dicarbonyl)(nitrosyl)iron complexes can also be reacted with electrophiles. Subjection to a,P-unsaturated carbonyl compounds leads to 5,E-unsaturated carbonyl compounds (Scheme 4-91). For this transformation, the allyliron complexes can even be generated in situ from haloalkenes and TBAFe. ... 

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