Coordination studies by Moessbauer spectroscopy of some metal(I)salts of the complex acid, hydrogen aquoethylenediaminetetraacetatoferrate(III)

Spijkerman, J. J.; Hall, L.H.; Lambert, Jack L.

doi:10.1021/ja01010a023

Cited by 25 publications

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“…This is not surprising because one of the carboxylic groups is very likely to become protonated in highly acidic solution, which results in dechelation of this carboxylic group from the coordinative bond and results in sixfold coordination of the central Fe 3+ . Such species have been observed by Spijkerman et al [33] -to species A2, although the quadrupole splitting for species A1 observed by us is smaller than that in ref. [33] Note that the quadrupole shift of A2 may not be directly related to quadrupole splitting data obtained from Lorentzian fits of nonmagnetic species because the relative orientation of the electric field gradient and the magnetic field is not known.…”

Section: Resultscontrasting

confidence: 50%

“…Such species have been observed by Spijkerman et al [33] -to species A2, although the quadrupole splitting for species A1 observed by us is smaller than that in ref. [33] Note that the quadrupole shift of A2 may not be directly related to quadrupole splitting data obtained from Lorentzian fits of nonmagnetic species because the relative orientation of the electric field gradient and the magnetic field is not known. We note here that Kanamori et al [34] have found hexacoordinate Fe III -EDTA species in solution only at even lower pH (in 1-2  HCl) using Raman spectroscopy, while at pH 1.2 they identified heptacoordinate species.…”

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confidence: 50%

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Mössbauer Investigation of Peroxo Species in the Iron(III)–EDTA–H₂O₂ System

et al. 2005

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The reaction of a diiron(III)–EDTA complex with H2O2 in alkaline medium is studied by Mössbauer spectroscopy in conjunction with the rapid‐freeze/quench technique in order to identify possible intermediate species during the formation and decomposition of the purple (EDTA)FeIII(η2‐O2)3– complex ion. Starting from the six‐coordinate [FeIIIEDTA]– species at acidic pH, it is demonstrated that mononuclear complexes formed at a pH of about 1 are convert into the diiron(III)–EDTA complex [(EDTA)FeIII‐O‐FeIII(EDTA)]4– upon raising the pH to around 10.4. H2O2 reacts with the diiron(III) complex to give peroxide/hydroperoxide related adducts. Initially, the reaction tears apart the dimers to form a peroxo adduct, namely the seven‐coordinate mononuclear [(EDTA)FeIII(η2‐O2)]3–, which is stable only at very high pH. The decomposition of this peroxo adduct gives two new species, which are reported for the first time. The Mössbauer parameters of these species suggest a six‐coordinate μ‐peroxodiiron(III) complex [(EDTA)FeIII‐(OO)‐FeIII(EDTA)]4– and a seven‐coordinate μ‐hydroxo‐μ‐peroxodiiron(III) complex [(EDTA)FeIII‐(OO)(OH)‐FeIII(EDTA)]5–. A badly resolved, extremely broad component is observed in the Mössbauer spectra during the conversion of the monomer to dimeric peroxo species, which may be attributed to the short‐lived [(EDTA)FeIII‐OO]3– or [(EDTA)FeIII‐OOH]2– intermediate species. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Section: Resultscontrasting

confidence: 50%

Section: Resultscontrasting

confidence: 50%

Mössbauer Investigation of Peroxo Species in the Iron(III)–EDTA–H₂O₂ System

et al. 2005

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“…Since aryl azides form iron complexes still retaining terminal and bridging carbonyls,5•6 we tested the suggestion of sulfonyl oxygen coordination with the metal by studying the decomposition of o-azidophenyl methyl sulfone (12) with metal carbonyls. The azide 12 was synthesized from o-aminophenyl methyl sulfone.17…”

Section: Resultsmentioning

confidence: 99%

Decomposition of sulfonyl azides and tert-butyl azidoformate by transition metal carbonyls

Abramovitch¹,

Knaus²,

Stowe³

1974

J. Org. Chem.

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“…They found the coordination numbers in aminopolycarboxylate complexes of the following ions were: Mn(II), seven (25); Fe(III), seven (26,30); Zr(IV), eight (27); Ln(III), eight to ten (28,29). Coordination numbers of seven and eight for Fe(II1) in aminopolycarboxylate complexes have also been proposed on the basis of Mossbauer studies (39,40). For large metal ions the strain in the ethylenic chelate ring increases rapidly with increasing size of the central ion.…”

Section: Cadmium (11)-dtpa Solutionsmentioning

confidence: 96%

Metal – Aminopolycarboxylic Acid Complexes. I. Studies of Lead(II) and Cadmium(II) Complexes with Diethylenetriaminepentaacetic Acid in Aqueous Solution by Proton Magnetic Resonance Spectroscopy

Letkeman¹,

Westmore²

1971

Can. J. Chem.

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Lead(I1) and cadmium(I1) each form a 1 :1 complex with DTPA. Nuclear magnetic resonance (n.m.r.) spectroscopy was used to show that each complex has three metal-nitrogen bonds and labile metal-oxygen bonds to terminal acetate groups. The latter lead to proton equivalence for the methylene protons of the terminal acetate groups of the lead complex, and near equivalence for those of the cadmium complex. The central carboxylate group is coordinated to the lead but not to the cadmium. Protonation occurs below pH 5.5 for the lead complex and occurs predominantly at a terminal nitrogen atom with consequent breaking of the metal-nitrogen bond. In the cadmium complex protonation occurs below p H 5 at the terminal nitrogen, breaking the metal-nitrogen bond, and also to almost the same extent at the central, uncoordinated carboxylate group. These differences in behavior of the lead and cadmium complexes are attributed to differences in ionic size. Possible structures are proposed and allowances are made for the possibility of coordination number greater than six. In the protonated complexes, structures and interconversion of protonated forms are discussed in the light of the observed simplification of the n.m.r. spectra.Le plomb(I1) et le cadmium(I1) forment chacun un complexe 1 :I avec le DTPA. La spectroscopie r.m.n. a ktk utiliske pour montrer que chaque complexe possede trois liaisons mktal-azote et des liaisons labiles mktal-oxygene aux groupes acktates terminaux. Ces dernikre rendent kquivalent les protons du groupe mkthylene situks sur les groupes acktates terminaux dans le complexe avec le plomb. Une quasikquivalence est obtenue pour le complexe avec le cadmium. Le groupe carboxylate central est coordonnk au plomb mais pas au cadmium. Dans le cas d'un complexe avec le plomb, la protonation se fait pour un p H infkrieur a 5.5 et de prkfkrence sur un atome d'azote terminalavec pour conskquence la rupture de la liaison m6tal-azote. Avec le complexe du cadmium, la protonation se situe en dessous de p H 5 sur l'atome d'azote terminal, provoquant la rupture de la liaison mktal-azote, et avec la m&me importance sur le groupe carboxylate central non coordonnk. Ces diffkrences de comportement entre le complexe du plomb et celui du cadmium sont attribuables a des diffkrences de grosseurs ioniques. Des structures possibles sont proposkes et il est tenu compte de la possibilitk de nombres de coordination supkrieurs a six. Dans les complexes protonks, les structures et I'interconversion des formes protonkes sont discutkes a la lumiere de la simplification observke dans les spectres r.m.n.Canadian Journal of Chemistry, 49, 2073Chemistry, 49, (1971 IntroductionThe use of proton magnetic resonance (p.m.r.) spectroscopy for the study of aqueous solutions of aminopolycarboxylic acids (1-5) and their diamagnetic complexes with metal ions (5-16) is wellestablished. In this paper we describe a systematic study of the behavior of the aqueous systems: lead(I1)-DTPA and cadmium(I1)-DTPA, where DTPA represents diethylenetriaminepentaac...

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Coordination studies by Moessbauer spectroscopy of some metal(I)salts of the complex acid, hydrogen aquoethylenediaminetetraacetatoferrate(III)

Cited by 25 publications

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Mössbauer Investigation of Peroxo Species in the Iron(III)–EDTA–H₂O₂ System

Mössbauer Investigation of Peroxo Species in the Iron(III)–EDTA–H₂O₂ System

Decomposition of sulfonyl azides and tert-butyl azidoformate by transition metal carbonyls

Metal – Aminopolycarboxylic Acid Complexes. I. Studies of Lead(II) and Cadmium(II) Complexes with Diethylenetriaminepentaacetic Acid in Aqueous Solution by Proton Magnetic Resonance Spectroscopy

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Coordination studies by Moessbauer spectroscopy of some metal(I)salts of the complex acid, hydrogen aquoethylenediaminetetraacetatoferrate(III)

Cited by 25 publications

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Mössbauer Investigation of Peroxo Species in the Iron(III)–EDTA–H2O2 System

Mössbauer Investigation of Peroxo Species in the Iron(III)–EDTA–H2O2 System

Decomposition of sulfonyl azides and tert-butyl azidoformate by transition metal carbonyls

Metal – Aminopolycarboxylic Acid Complexes. I. Studies of Lead(II) and Cadmium(II) Complexes with Diethylenetriaminepentaacetic Acid in Aqueous Solution by Proton Magnetic Resonance Spectroscopy

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Mössbauer Investigation of Peroxo Species in the Iron(III)–EDTA–H₂O₂ System

Mössbauer Investigation of Peroxo Species in the Iron(III)–EDTA–H₂O₂ System