Valence states and structure of mixed-valence dinuclear iron(II,III) complexes [Fe2(2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol) (L)2](BF4)2

Yonezo Maeda, Akiko Ishida, Masaaki Ohba, Shinji Sugihara, Shinya Hayami

研究成果: ジャーナルへの寄稿記事

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Mixed-valence dinuclear iron(II,III) complexes, FeIIFeIII(bpmp)(L)2] (BF4)2, have been prepared, and the structures, electrochemical properties and rates of intramolecular electron transfer of the complexes have been examined, where Hbpmp represents 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol and L is 2-methoxybenzoate (omb), 3-methoxybenzoate (mmb), 4-methoxybenzoate (pmb), 3,5-dimethoxybenzoate (dmb), 3,4,5-trimethoxybenzoate (tmb) or 4-biphenylcarboxylate (bpc). It turns out from the Móssbauer spectra that the valence states of iron atoms of [FeIIFeIII(bpmp)(omb)2] (BF4)2, [FeIIFeIII(bpmp)(pmb)2] (BF4)2, [FeIIFeIII(bpmp)(tmb)2] (BF4)2 and [FeIIFeIII(bpmp)(bpc)2] (ClO4)2 are localized at 78 K and delocalized at 293 K. The temperature dependence of the spectra is interpreted by assuming intramolecular electron transfer between two energetically equivalent vibronic states FeAIIFeBIII and FeAIIFeBIII. The Mössbauer spectra of [FeIIFeIII(bpmp)(dmb)2] (BF4)2 show the superposition of the relaxation spectrum between iron(II) and iron(III), and of the spectrum of the average valence states at 293 K; the average valence states are partly observed even at 78 K. The valence states of [FeIIFeIII(bpmp)(mmb)2] (BF4)2 are localized over the temperature range from 78 K to 293 K. The single-crystal X-ray structure of [FeIIFeIII(bpmp)(bpc)2] (ClO4)2 was determined at 293 K. The complex crystallizes in the orthorhombic space group Fdd2, which has a unit cell of a = 27.056(1) Å, b = 42.652(0) Å, c = 12.151(0) Å and Z = 8. A refinement was performed with 2340 unique reflections [I > 3σ(I)] to give R = 0.085, Rw = 0.099. The two iron atoms are located symmetrically to a C2 axis, which presents in the molecule, and are crystallographically equivalent. The mean Fe-O length is intermediate between the FeII-O and FeIII-O values, indicating that both iron atoms are in an averaged valence state.

元の言語英語
ページ(範囲)2441-2448
ページ数8
ジャーナルBulletin of the Chemical Society of Japan
75
発行部数11
DOI
出版物ステータス出版済み - 11 1 2002

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Iron
Atoms
Electrons
2,6-bis(bis(2-pyridylmethyl)aminomethyl)-4-methylphenol
Electrochemical properties
Single crystals
X rays
Temperature
Molecules
perchlorate
2-methoxybenzoic acid

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

これを引用

Valence states and structure of mixed-valence dinuclear iron(II,III) complexes [Fe2(2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol) (L)2](BF4)2. / Maeda, Yonezo; Ishida, Akiko; Ohba, Masaaki; Sugihara, Shinji; Hayami, Shinya.

:: Bulletin of the Chemical Society of Japan, 巻 75, 番号 11, 01.11.2002, p. 2441-2448.

研究成果: ジャーナルへの寄稿記事

@article{d523deeed4a145cbae29206dd2bb34c5,
title = "Valence states and structure of mixed-valence dinuclear iron(II,III) complexes [Fe2(2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol) (L)2](BF4)2",
abstract = "Mixed-valence dinuclear iron(II,III) complexes, FeIIFeIII(bpmp)(L)2] (BF4)2, have been prepared, and the structures, electrochemical properties and rates of intramolecular electron transfer of the complexes have been examined, where Hbpmp represents 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol and L is 2-methoxybenzoate (omb), 3-methoxybenzoate (mmb), 4-methoxybenzoate (pmb), 3,5-dimethoxybenzoate (dmb), 3,4,5-trimethoxybenzoate (tmb) or 4-biphenylcarboxylate (bpc). It turns out from the M{\'o}ssbauer spectra that the valence states of iron atoms of [FeIIFeIII(bpmp)(omb)2] (BF4)2, [FeIIFeIII(bpmp)(pmb)2] (BF4)2, [FeIIFeIII(bpmp)(tmb)2] (BF4)2 and [FeIIFeIII(bpmp)(bpc)2] (ClO4)2 are localized at 78 K and delocalized at 293 K. The temperature dependence of the spectra is interpreted by assuming intramolecular electron transfer between two energetically equivalent vibronic states FeAIIFeBIII and FeAIIFeBIII. The M{\"o}ssbauer spectra of [FeIIFeIII(bpmp)(dmb)2] (BF4)2 show the superposition of the relaxation spectrum between iron(II) and iron(III), and of the spectrum of the average valence states at 293 K; the average valence states are partly observed even at 78 K. The valence states of [FeIIFeIII(bpmp)(mmb)2] (BF4)2 are localized over the temperature range from 78 K to 293 K. The single-crystal X-ray structure of [FeIIFeIII(bpmp)(bpc)2] (ClO4)2 was determined at 293 K. The complex crystallizes in the orthorhombic space group Fdd2, which has a unit cell of a = 27.056(1) {\AA}, b = 42.652(0) {\AA}, c = 12.151(0) {\AA} and Z = 8. A refinement was performed with 2340 unique reflections [I > 3σ(I)] to give R = 0.085, Rw = 0.099. The two iron atoms are located symmetrically to a C2 axis, which presents in the molecule, and are crystallographically equivalent. The mean Fe-O length is intermediate between the FeII-O and FeIII-O values, indicating that both iron atoms are in an averaged valence state.",
author = "Yonezo Maeda and Akiko Ishida and Masaaki Ohba and Shinji Sugihara and Shinya Hayami",
year = "2002",
month = "11",
day = "1",
doi = "10.1246/bcsj.75.2441",
language = "English",
volume = "75",
pages = "2441--2448",
journal = "Bulletin of the Chemical Society of Japan",
issn = "0009-2673",
publisher = "The Chemical Society of Japan",
number = "11",

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TY - JOUR

T1 - Valence states and structure of mixed-valence dinuclear iron(II,III) complexes [Fe2(2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol) (L)2](BF4)2

AU - Maeda, Yonezo

AU - Ishida, Akiko

AU - Ohba, Masaaki

AU - Sugihara, Shinji

AU - Hayami, Shinya

PY - 2002/11/1

Y1 - 2002/11/1

N2 - Mixed-valence dinuclear iron(II,III) complexes, FeIIFeIII(bpmp)(L)2] (BF4)2, have been prepared, and the structures, electrochemical properties and rates of intramolecular electron transfer of the complexes have been examined, where Hbpmp represents 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol and L is 2-methoxybenzoate (omb), 3-methoxybenzoate (mmb), 4-methoxybenzoate (pmb), 3,5-dimethoxybenzoate (dmb), 3,4,5-trimethoxybenzoate (tmb) or 4-biphenylcarboxylate (bpc). It turns out from the Móssbauer spectra that the valence states of iron atoms of [FeIIFeIII(bpmp)(omb)2] (BF4)2, [FeIIFeIII(bpmp)(pmb)2] (BF4)2, [FeIIFeIII(bpmp)(tmb)2] (BF4)2 and [FeIIFeIII(bpmp)(bpc)2] (ClO4)2 are localized at 78 K and delocalized at 293 K. The temperature dependence of the spectra is interpreted by assuming intramolecular electron transfer between two energetically equivalent vibronic states FeAIIFeBIII and FeAIIFeBIII. The Mössbauer spectra of [FeIIFeIII(bpmp)(dmb)2] (BF4)2 show the superposition of the relaxation spectrum between iron(II) and iron(III), and of the spectrum of the average valence states at 293 K; the average valence states are partly observed even at 78 K. The valence states of [FeIIFeIII(bpmp)(mmb)2] (BF4)2 are localized over the temperature range from 78 K to 293 K. The single-crystal X-ray structure of [FeIIFeIII(bpmp)(bpc)2] (ClO4)2 was determined at 293 K. The complex crystallizes in the orthorhombic space group Fdd2, which has a unit cell of a = 27.056(1) Å, b = 42.652(0) Å, c = 12.151(0) Å and Z = 8. A refinement was performed with 2340 unique reflections [I > 3σ(I)] to give R = 0.085, Rw = 0.099. The two iron atoms are located symmetrically to a C2 axis, which presents in the molecule, and are crystallographically equivalent. The mean Fe-O length is intermediate between the FeII-O and FeIII-O values, indicating that both iron atoms are in an averaged valence state.

AB - Mixed-valence dinuclear iron(II,III) complexes, FeIIFeIII(bpmp)(L)2] (BF4)2, have been prepared, and the structures, electrochemical properties and rates of intramolecular electron transfer of the complexes have been examined, where Hbpmp represents 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol and L is 2-methoxybenzoate (omb), 3-methoxybenzoate (mmb), 4-methoxybenzoate (pmb), 3,5-dimethoxybenzoate (dmb), 3,4,5-trimethoxybenzoate (tmb) or 4-biphenylcarboxylate (bpc). It turns out from the Móssbauer spectra that the valence states of iron atoms of [FeIIFeIII(bpmp)(omb)2] (BF4)2, [FeIIFeIII(bpmp)(pmb)2] (BF4)2, [FeIIFeIII(bpmp)(tmb)2] (BF4)2 and [FeIIFeIII(bpmp)(bpc)2] (ClO4)2 are localized at 78 K and delocalized at 293 K. The temperature dependence of the spectra is interpreted by assuming intramolecular electron transfer between two energetically equivalent vibronic states FeAIIFeBIII and FeAIIFeBIII. The Mössbauer spectra of [FeIIFeIII(bpmp)(dmb)2] (BF4)2 show the superposition of the relaxation spectrum between iron(II) and iron(III), and of the spectrum of the average valence states at 293 K; the average valence states are partly observed even at 78 K. The valence states of [FeIIFeIII(bpmp)(mmb)2] (BF4)2 are localized over the temperature range from 78 K to 293 K. The single-crystal X-ray structure of [FeIIFeIII(bpmp)(bpc)2] (ClO4)2 was determined at 293 K. The complex crystallizes in the orthorhombic space group Fdd2, which has a unit cell of a = 27.056(1) Å, b = 42.652(0) Å, c = 12.151(0) Å and Z = 8. A refinement was performed with 2340 unique reflections [I > 3σ(I)] to give R = 0.085, Rw = 0.099. The two iron atoms are located symmetrically to a C2 axis, which presents in the molecule, and are crystallographically equivalent. The mean Fe-O length is intermediate between the FeII-O and FeIII-O values, indicating that both iron atoms are in an averaged valence state.

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