Instability of the nitrite/iron(III) porphyrinate system

Finnegan, Michael G.; Lappin, A. Graham; Scheidt, W. Robert

doi:10.1021/ic00327a008

Cited by 69 publications

(74 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The instability of stoichiometric ratios of Fe(P)(X) and nitrite (where X = easily displaceable anion) was similar to the work of Finnegan et al [5], where they observed a slow decomposition of the mono-nitrite complex. Unlike their work, though, we were unable to detect the disproportionation of nitrite to ferrous-NO and nitrate.…”

supporting

confidence: 81%

“…When the concentrations of Fe(OEP)(NO3) and NaNO2 were both 1 mM, the highspin spectrum disappeared and was replaced by a low-spin ferric porphyrin spectrum. If an oxygen transfer reaction occurred under the conditions of this experiment to form Fe(OEP)(NO) and Fe(OEP)(NO3), the latter complex should be observed in the proton NMR [5]. In addition, the experiments were completed rapidly enough so that there was no evidence for the μ-oxo complex (CH2: 6.04 and 5.08 ppm [19]), which was the long term decomposition product observed in our work by visible spectroscopy.…”

mentioning

confidence: 94%

“…Finnegan et al [5] found that ferric porphyrins slowly reacted with nitrite to lead to Fe(P)(NO) and Fe(P)(NO3). O'Shea et al [6] observed that ferric nitrite complexes accessed by following the link in the citation at the bottom of the page.…”

Section: Introductionmentioning

confidence: 99%

“…Many of the experiments by Finnegan et al [5] were carried out in methylene chloride, creating some ambiguities as to whether the reactions were due to nitrite or organonitro compounds. Some of the differences may also be due equilibrium shifts caused by the presence or absence of halide ions (e.g., chloride as the axial ligand).…”

mentioning

confidence: 99%

See 3 more Smart Citations

Electrochemistry and spectroelectrochemistry of iron porphyrins in the presence of nitrite

Wei

2001

Inorganica Chimica Acta

View full text Add to dashboard Cite

Abstract:The reaction of nitrite with ferric and ferrous porphyrins was examined using visible, infrared and NMR spectroscopy. Solutions of either ferric or ferrous porphyrin were stable in the presence of nitrite, with only complexation reactions being observed. Under voltammetric conditions, though, a rapid reaction was observed between nitrite and iron porphyrins to form the nitrosyl complex, Fe(P)(NO), where P = porphyrin. The products of the reduction of ferric porphyrins in the presence of nitrite were confirmed by visible spectroelectrochemistry to be Fe(P)(NO) and [Fe(P)]2O. Visible, NMR and infrared spectroscopy were used to rule out the formation of Fe(P)(NO) by the iron catalyzed disproportionation of nitrite.NOT THE PUBLISHED VERSION; this is the author's final, peer-reviewed manuscript. The published version may be accessed by following the link in the citation at the bottom of the page.Inorganica Chimica Acta, Vol. 314, No. 1-2 (March 2001): pg. 49-57. Publisher's link. This article is © Elsevier and permission has been granted for this version to appear in e-Publications@Marquette. Elsevier does not grant permission for this article to be further copied/distributed or hosted elsewhere without the express permission from Elsevier. 2A reaction between iron porphyrins and nitrite only occurred by the presence of both oxidation states (ferric/ferrous). The kinetics of the reaction was monitored by visible spectroscopy, and the reaction was found to be firstorder with respect to Fe(OEP)(Cl) and Fe(OEP). The products were the same as those observed in the spectroelectrochemical experiment. The rate was not strongly dependent upon the concentration of nitrite, indicating that the coordinated, not the free nitrite, was the reaction species. The observed kinetics was consistent with a mixed oxidation state nitrite bridged intermediate, which carried out the oxygen transfer reaction from nitrite to the iron porphyrin. The effect of nitrite coordination on the reaction rate was examined.

show abstract

supporting

confidence: 81%

mentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

See 2 more Smart Citations

Electrochemistry and spectroelectrochemistry of iron porphyrins in the presence of nitrite

Wei

2001

Inorganica Chimica Acta

View full text Add to dashboard Cite

show abstract

“…Further, I would take notice of two bodies of work that have not been discussed in this paper, work on the other oxynitrogen-ligated porphyrins (the ligands NO 2 − and NO 3 − ) [112][113][114][115][116][117][118][119][120][121][122][123][124] and the work on the characterization of π-cation radical complexes [125][126][127][128][129][130][131][132][133][134][135][136][137][138][139]. Diagram Illustrating the effect of axial ligand orientation on the axial bond distances in iron (III) species.…”

Section: Discussionmentioning

confidence: 99%

Explorations in metalloporphyrin stereochemistry, physical properties and beyond

Scheidt

2008

J. Porphyrins Phthalocyanines

Self Cite

View full text Add to dashboard Cite

A review of selected portions of our work in the area of porphyrin structure and physical characterization is presented. Topics covered include early work on periodic trends in first row transtion metalloporphyrins, a survey of electronic structure of iron derivatives including spin-state trends, ligand orientation effects and the elucidtion of unusual low-spin states for iron(II). A discussion of the different tlypes of high-spin iron(II) complexes and the effects of hydrogen bonding is given. A survey of nitric oxide (NO) derivatives is presented as well as a brief introduction into the use of nuclear resonance vibrational spectroscopy for the study of iron porphyrins and heme proteins.

show abstract

Synthesis, Properties and Crystal Structure of Bis(tetra(n-butyl)ammonium) Bisnitrophthalocyaninatoruthenate(II)

Sievertsen

Weidemann

Hückstädt

et al. 1997

J. Porphyrins Phthalocyanines

View full text Add to dashboard Cite

Tetra(n-butyl)ammonium nitrite reacts with ‘dichlorophthalocyaninatoruthenium(III) acid’ to yield bis(tetra(n-butyl)ammonium) bisnitrophthalocyaninatoruthenate(II). It crystallizes monoclinic with crystal data: a = 15.114(4) Å, b = 22.34(3) Å, c = 18.206 (11) Å, β = 90.88(5)°; space group P1 21/n 1, Z = 4, and its X-ray crystal structure has been determined. Ru is located in the centre of the slightly distorted phthalocyaninate dianion, and is coordinated to two nitrite ions through their nitrogen (N) atoms in a staggered trans-configuration. The average Ru - N p ( Np pyrrolic N atoms) and Ru -N distance is 1.978(6) and 2.068(5) Å, respectively. The electrochemical and spectroscopic properties (IR, resonance Raman, UV/vis) of the compound are in full agreement with its molecular structure.

show abstract

Instability of the nitrite/iron(III) porphyrinate system

Cited by 69 publications

References 0 publications

Electrochemistry and spectroelectrochemistry of iron porphyrins in the presence of nitrite

Electrochemistry and spectroelectrochemistry of iron porphyrins in the presence of nitrite

Explorations in metalloporphyrin stereochemistry, physical properties and beyond

Synthesis, Properties and Crystal Structure of Bis(tetra(n-butyl)ammonium) Bisnitrophthalocyaninatoruthenate(II)

Contact Info

Product

Resources

About