Oxalate-Bridged Dinuclear Cr(III)-M(II) (M = Cu, Ni, Co, Fe, Mn) Complexes: Synthesis, Structure, and Magnetism

Masaaki Ohba, Hiroko Tamaki, Naohide Matsumoto, Hisashi Ōkawa

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Abstract

The following oxalate-bridged heterodinuclear Cr(III)-M(II) (M = Cu, Ni, Co, Fe, Mn) complexes have been synthesized: [Cr(salen)(ox)Cu(acpy)] (1) (salen = N,N′-ethylenebis(salicylideneaminate), ox2− = oxalate ion, acpy = N-acetylacetonylidene-N-(2-pyridylethyl)aminate) and [Cr(salen)(ox)M(taea)](BPh4) (M = Ni (2), Co (3), Fe (4), Mn (5)) (taea = tris(2-aminoethyl)amine). The [Cr(salen)(ox)Cu(acpy)]2DMFN·MeOH (1′) complex crystallizes in the monoclinic system of the space group P21/n with a = 16.429(6) Å, b = 25.303(14) Å, c = 10.191(4) Å, β = 109.78(2)°, V = 3986(3) Å3, and Z = 4. The refinement converges with R = 0.079 and Rw = 0.071 based on 3327 reflections with |Fo| ≥ 3σ(|Fo|). The complex has an oxalate-bridged dinuclear Cr(III)-Cu(II) core with a Cr⋯Cu distance of 5.482(3) Å. The Cr(III) has a cis-β octahedral geometry with the tetradentate salen in the folded form and a bidentate oxalate group. The geometry around the Cu(II) ion is square-pyramidal with the three donor atoms of acpy and one of the oxalate oxygens at the basal plane and the other oxygen of the oxalate group at the apex. Magnetic investigations of 1–5 in the 4.2–300 K temperature range reveal a ferromagnetic interaction between the Cr(III) and M(II) ions for all the complexes. On the basis of the spin Hamiltonian, Ĥ = −JSCr·SM, the values for the spin coupling constant J were estimated to be +2.8, +4.6, +1.3, +0.8, and +0.5 cm−1 for 1–5, respectively. The relative magnitude of the J values is explained by the σ- and π-pathways through the oxalate bridge. The correlation between the J values of 1–5 and the phase-transition temperatures, TC, of the ferromagnetic {NBu4[MCr(ox)3]}x (M = Cu, Ni, Co, Fe, Mn) is discussed based on Heisenberg's ferromagnet model.

Original languageEnglish
Pages (from-to)5385-5390
Number of pages6
JournalInorganic chemistry
Volume32
Issue number23
DOIs
Publication statusPublished - Jan 1 1993

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Oxalates
Magnetism
oxalates
synthesis
Ions
Oxygen
Hamiltonians
ions
Geometry
oxygen
geometry
amines
apexes
Phase transitions
transition temperature
disalicylaldehyde ethylenediamine
Atoms
atoms

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Oxalate-Bridged Dinuclear Cr(III)-M(II) (M = Cu, Ni, Co, Fe, Mn) Complexes : Synthesis, Structure, and Magnetism. / Ohba, Masaaki; Tamaki, Hiroko; Matsumoto, Naohide; Ōkawa, Hisashi.

In: Inorganic chemistry, Vol. 32, No. 23, 01.01.1993, p. 5385-5390.

Research output: Contribution to journalArticle

Ohba, Masaaki ; Tamaki, Hiroko ; Matsumoto, Naohide ; Ōkawa, Hisashi. / Oxalate-Bridged Dinuclear Cr(III)-M(II) (M = Cu, Ni, Co, Fe, Mn) Complexes : Synthesis, Structure, and Magnetism. In: Inorganic chemistry. 1993 ; Vol. 32, No. 23. pp. 5385-5390.
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title = "Oxalate-Bridged Dinuclear Cr(III)-M(II) (M = Cu, Ni, Co, Fe, Mn) Complexes: Synthesis, Structure, and Magnetism",
abstract = "The following oxalate-bridged heterodinuclear Cr(III)-M(II) (M = Cu, Ni, Co, Fe, Mn) complexes have been synthesized: [Cr(salen)(ox)Cu(acpy)] (1) (salen = N,N′-ethylenebis(salicylideneaminate), ox2− = oxalate ion, acpy = N-acetylacetonylidene-N-(2-pyridylethyl)aminate) and [Cr(salen)(ox)M(taea)](BPh4) (M = Ni (2), Co (3), Fe (4), Mn (5)) (taea = tris(2-aminoethyl)amine). The [Cr(salen)(ox)Cu(acpy)]2DMFN·MeOH (1′) complex crystallizes in the monoclinic system of the space group P21/n with a = 16.429(6) {\AA}, b = 25.303(14) {\AA}, c = 10.191(4) {\AA}, β = 109.78(2)°, V = 3986(3) {\AA}3, and Z = 4. The refinement converges with R = 0.079 and Rw = 0.071 based on 3327 reflections with |Fo| ≥ 3σ(|Fo|). The complex has an oxalate-bridged dinuclear Cr(III)-Cu(II) core with a Cr⋯Cu distance of 5.482(3) {\AA}. The Cr(III) has a cis-β octahedral geometry with the tetradentate salen in the folded form and a bidentate oxalate group. The geometry around the Cu(II) ion is square-pyramidal with the three donor atoms of acpy and one of the oxalate oxygens at the basal plane and the other oxygen of the oxalate group at the apex. Magnetic investigations of 1–5 in the 4.2–300 K temperature range reveal a ferromagnetic interaction between the Cr(III) and M(II) ions for all the complexes. On the basis of the spin Hamiltonian, Ĥ = −JSCr·SM, the values for the spin coupling constant J were estimated to be +2.8, +4.6, +1.3, +0.8, and +0.5 cm−1 for 1–5, respectively. The relative magnitude of the J values is explained by the σ- and π-pathways through the oxalate bridge. The correlation between the J values of 1–5 and the phase-transition temperatures, TC, of the ferromagnetic {NBu4[MCr(ox)3]}x (M = Cu, Ni, Co, Fe, Mn) is discussed based on Heisenberg's ferromagnet model.",
author = "Masaaki Ohba and Hiroko Tamaki and Naohide Matsumoto and Hisashi Ōkawa",
year = "1993",
month = "1",
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journal = "Inorganic Chemistry",
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publisher = "American Chemical Society",
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T1 - Oxalate-Bridged Dinuclear Cr(III)-M(II) (M = Cu, Ni, Co, Fe, Mn) Complexes

T2 - Synthesis, Structure, and Magnetism

AU - Ohba, Masaaki

AU - Tamaki, Hiroko

AU - Matsumoto, Naohide

AU - Ōkawa, Hisashi

PY - 1993/1/1

Y1 - 1993/1/1

N2 - The following oxalate-bridged heterodinuclear Cr(III)-M(II) (M = Cu, Ni, Co, Fe, Mn) complexes have been synthesized: [Cr(salen)(ox)Cu(acpy)] (1) (salen = N,N′-ethylenebis(salicylideneaminate), ox2− = oxalate ion, acpy = N-acetylacetonylidene-N-(2-pyridylethyl)aminate) and [Cr(salen)(ox)M(taea)](BPh4) (M = Ni (2), Co (3), Fe (4), Mn (5)) (taea = tris(2-aminoethyl)amine). The [Cr(salen)(ox)Cu(acpy)]2DMFN·MeOH (1′) complex crystallizes in the monoclinic system of the space group P21/n with a = 16.429(6) Å, b = 25.303(14) Å, c = 10.191(4) Å, β = 109.78(2)°, V = 3986(3) Å3, and Z = 4. The refinement converges with R = 0.079 and Rw = 0.071 based on 3327 reflections with |Fo| ≥ 3σ(|Fo|). The complex has an oxalate-bridged dinuclear Cr(III)-Cu(II) core with a Cr⋯Cu distance of 5.482(3) Å. The Cr(III) has a cis-β octahedral geometry with the tetradentate salen in the folded form and a bidentate oxalate group. The geometry around the Cu(II) ion is square-pyramidal with the three donor atoms of acpy and one of the oxalate oxygens at the basal plane and the other oxygen of the oxalate group at the apex. Magnetic investigations of 1–5 in the 4.2–300 K temperature range reveal a ferromagnetic interaction between the Cr(III) and M(II) ions for all the complexes. On the basis of the spin Hamiltonian, Ĥ = −JSCr·SM, the values for the spin coupling constant J were estimated to be +2.8, +4.6, +1.3, +0.8, and +0.5 cm−1 for 1–5, respectively. The relative magnitude of the J values is explained by the σ- and π-pathways through the oxalate bridge. The correlation between the J values of 1–5 and the phase-transition temperatures, TC, of the ferromagnetic {NBu4[MCr(ox)3]}x (M = Cu, Ni, Co, Fe, Mn) is discussed based on Heisenberg's ferromagnet model.

AB - The following oxalate-bridged heterodinuclear Cr(III)-M(II) (M = Cu, Ni, Co, Fe, Mn) complexes have been synthesized: [Cr(salen)(ox)Cu(acpy)] (1) (salen = N,N′-ethylenebis(salicylideneaminate), ox2− = oxalate ion, acpy = N-acetylacetonylidene-N-(2-pyridylethyl)aminate) and [Cr(salen)(ox)M(taea)](BPh4) (M = Ni (2), Co (3), Fe (4), Mn (5)) (taea = tris(2-aminoethyl)amine). The [Cr(salen)(ox)Cu(acpy)]2DMFN·MeOH (1′) complex crystallizes in the monoclinic system of the space group P21/n with a = 16.429(6) Å, b = 25.303(14) Å, c = 10.191(4) Å, β = 109.78(2)°, V = 3986(3) Å3, and Z = 4. The refinement converges with R = 0.079 and Rw = 0.071 based on 3327 reflections with |Fo| ≥ 3σ(|Fo|). The complex has an oxalate-bridged dinuclear Cr(III)-Cu(II) core with a Cr⋯Cu distance of 5.482(3) Å. The Cr(III) has a cis-β octahedral geometry with the tetradentate salen in the folded form and a bidentate oxalate group. The geometry around the Cu(II) ion is square-pyramidal with the three donor atoms of acpy and one of the oxalate oxygens at the basal plane and the other oxygen of the oxalate group at the apex. Magnetic investigations of 1–5 in the 4.2–300 K temperature range reveal a ferromagnetic interaction between the Cr(III) and M(II) ions for all the complexes. On the basis of the spin Hamiltonian, Ĥ = −JSCr·SM, the values for the spin coupling constant J were estimated to be +2.8, +4.6, +1.3, +0.8, and +0.5 cm−1 for 1–5, respectively. The relative magnitude of the J values is explained by the σ- and π-pathways through the oxalate bridge. The correlation between the J values of 1–5 and the phase-transition temperatures, TC, of the ferromagnetic {NBu4[MCr(ox)3]}x (M = Cu, Ni, Co, Fe, Mn) is discussed based on Heisenberg's ferromagnet model.

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