Tetranuclear mixed-metal MII2CuII2 complexes derived from a phenol-based macrocyclic ligand having two N(amine)2O2 and two N(imine)2O2 metal-binding sites

Y. Nakamura, M. Yonemura, K. Arimura, N. Usuki, Masaaki Ohba, H. Okawa

Research output: Contribution to journalArticle

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Abstract

The reaction of N,N′-dimethyl-N,N′-ethylenebis (5-bromo-3-formyl-2-hydroxybenzylaminato)copper(II) with ethylenediamine in aqueous DMF with excess perchloric acid resulted in the [2:2] cyclic condensation of the constituents, providing the dinuclear CuII complex [Cu2(H2R)](ClO4)2. It crystallizes in the monoclinic space group P21/c, with a = 19.603(3) Å, b = 13.370(2) Å, c = 21.072(3) Å, β = 98.87(1)° V = 5456(1) Å3, and Z = 4. The ligand R4- has two N(amine)2O2 and two N(imine)2O2 metal-binding sites sharing two phenolic oxygens, and [Cu2(H2R)](ClO4)2 has the two CuII ions in the N(imine)2O2 sites and two protons in the N(amine)2O2 sites. [Cu2(H2R)](ClO4)2 was converted by neutralization into [Cu2(R)], from which mixed-metal CuII2MII2 complexes [Cu2M2(R)Cl4] (M = CoII, NiII, ZnII) were derived. [Cu2Co2 (R)Cl4]·2CHCl3·H2O crystallizes in the monoclinic space group C2/c, with a = 32.514(3) Å, b = 12.246(3) Å, c = 19.827(2) Å, β = 126.082(1)° V = 6380(1) Å3, and Z = 4. [Cu2Zn2(R)Cl4] ·2CHCl3·H2O crystallizes in the monoclinic space group C2/c, with a = 32.53(1) Å, b = 12.242(2) Å, c = 19.729(9) Å, β = 126.03(3)°, V = 6354(4) Å3, and Z = 4. The two complexes are isotructural and have a dimer-of-dimers structure with two separated CuIIMII units. In each dinuclear unit, the CuII is bound to the N(imine)2O2 site and the MII is bonded to a phenolic oxygen and two nitrogens of the N(amine)2O2 site. The CuII and MII ions are bridged by a phenolic oxygen and an exogenous chloride ion. The CuII2NiII2 complex has a defect double-cubane structure. Cryomagnetic studies for the CuII2CoII2 complex indicate an antiferromagnetic spin-exchange interaction within each dinuclear CuIICoII unit (J = -9.5 cm-1 based on H = -2JSCuSCo). The CuII2NiII2 complex shows a weak antiferromagnetic interaction between the adjacent CuII and NiII ions (-3.5 cm-1) and a weak ferromagnetic interaction between the two NiII ions (+2.0 cm-1.

Original languageEnglish
Pages (from-to)3739-3744
Number of pages6
JournalInorganic chemistry
Volume40
Issue number15
DOIs
Publication statusPublished - Jul 16 2001

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Imines
Coordination Complexes
Phenol
phenols
imines
Amines
amines
Metals
Binding Sites
Ions
Ligands
ligands
ethylenediamine
metals
Oxygen
ions
Dimers
oxygen
dimers
cubane

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Tetranuclear mixed-metal MII2CuII2 complexes derived from a phenol-based macrocyclic ligand having two N(amine)2O2 and two N(imine)2O2 metal-binding sites. / Nakamura, Y.; Yonemura, M.; Arimura, K.; Usuki, N.; Ohba, Masaaki; Okawa, H.

In: Inorganic chemistry, Vol. 40, No. 15, 16.07.2001, p. 3739-3744.

Research output: Contribution to journalArticle

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title = "Tetranuclear mixed-metal MII2CuII2 complexes derived from a phenol-based macrocyclic ligand having two N(amine)2O2 and two N(imine)2O2 metal-binding sites",
abstract = "The reaction of N,N′-dimethyl-N,N′-ethylenebis (5-bromo-3-formyl-2-hydroxybenzylaminato)copper(II) with ethylenediamine in aqueous DMF with excess perchloric acid resulted in the [2:2] cyclic condensation of the constituents, providing the dinuclear CuII complex [Cu2(H2R)](ClO4)2. It crystallizes in the monoclinic space group P21/c, with a = 19.603(3) {\AA}, b = 13.370(2) {\AA}, c = 21.072(3) {\AA}, β = 98.87(1)° V = 5456(1) {\AA}3, and Z = 4. The ligand R4- has two N(amine)2O2 and two N(imine)2O2 metal-binding sites sharing two phenolic oxygens, and [Cu2(H2R)](ClO4)2 has the two CuII ions in the N(imine)2O2 sites and two protons in the N(amine)2O2 sites. [Cu2(H2R)](ClO4)2 was converted by neutralization into [Cu2(R)], from which mixed-metal CuII2MII2 complexes [Cu2M2(R)Cl4] (M = CoII, NiII, ZnII) were derived. [Cu2Co2 (R)Cl4]·2CHCl3·H2O crystallizes in the monoclinic space group C2/c, with a = 32.514(3) {\AA}, b = 12.246(3) {\AA}, c = 19.827(2) {\AA}, β = 126.082(1)° V = 6380(1) {\AA}3, and Z = 4. [Cu2Zn2(R)Cl4] ·2CHCl3·H2O crystallizes in the monoclinic space group C2/c, with a = 32.53(1) {\AA}, b = 12.242(2) {\AA}, c = 19.729(9) {\AA}, β = 126.03(3)°, V = 6354(4) {\AA}3, and Z = 4. The two complexes are isotructural and have a dimer-of-dimers structure with two separated CuIIMII units. In each dinuclear unit, the CuII is bound to the N(imine)2O2 site and the MII is bonded to a phenolic oxygen and two nitrogens of the N(amine)2O2 site. The CuII and MII ions are bridged by a phenolic oxygen and an exogenous chloride ion. The CuII2NiII2 complex has a defect double-cubane structure. Cryomagnetic studies for the CuII2CoII2 complex indicate an antiferromagnetic spin-exchange interaction within each dinuclear CuIICoII unit (J = -9.5 cm-1 based on H = -2JSCuSCo). The CuII2NiII2 complex shows a weak antiferromagnetic interaction between the adjacent CuII and NiII ions (-3.5 cm-1) and a weak ferromagnetic interaction between the two NiII ions (+2.0 cm-1.",
author = "Y. Nakamura and M. Yonemura and K. Arimura and N. Usuki and Masaaki Ohba and H. Okawa",
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TY - JOUR

T1 - Tetranuclear mixed-metal MII2CuII2 complexes derived from a phenol-based macrocyclic ligand having two N(amine)2O2 and two N(imine)2O2 metal-binding sites

AU - Nakamura, Y.

AU - Yonemura, M.

AU - Arimura, K.

AU - Usuki, N.

AU - Ohba, Masaaki

AU - Okawa, H.

PY - 2001/7/16

Y1 - 2001/7/16

N2 - The reaction of N,N′-dimethyl-N,N′-ethylenebis (5-bromo-3-formyl-2-hydroxybenzylaminato)copper(II) with ethylenediamine in aqueous DMF with excess perchloric acid resulted in the [2:2] cyclic condensation of the constituents, providing the dinuclear CuII complex [Cu2(H2R)](ClO4)2. It crystallizes in the monoclinic space group P21/c, with a = 19.603(3) Å, b = 13.370(2) Å, c = 21.072(3) Å, β = 98.87(1)° V = 5456(1) Å3, and Z = 4. The ligand R4- has two N(amine)2O2 and two N(imine)2O2 metal-binding sites sharing two phenolic oxygens, and [Cu2(H2R)](ClO4)2 has the two CuII ions in the N(imine)2O2 sites and two protons in the N(amine)2O2 sites. [Cu2(H2R)](ClO4)2 was converted by neutralization into [Cu2(R)], from which mixed-metal CuII2MII2 complexes [Cu2M2(R)Cl4] (M = CoII, NiII, ZnII) were derived. [Cu2Co2 (R)Cl4]·2CHCl3·H2O crystallizes in the monoclinic space group C2/c, with a = 32.514(3) Å, b = 12.246(3) Å, c = 19.827(2) Å, β = 126.082(1)° V = 6380(1) Å3, and Z = 4. [Cu2Zn2(R)Cl4] ·2CHCl3·H2O crystallizes in the monoclinic space group C2/c, with a = 32.53(1) Å, b = 12.242(2) Å, c = 19.729(9) Å, β = 126.03(3)°, V = 6354(4) Å3, and Z = 4. The two complexes are isotructural and have a dimer-of-dimers structure with two separated CuIIMII units. In each dinuclear unit, the CuII is bound to the N(imine)2O2 site and the MII is bonded to a phenolic oxygen and two nitrogens of the N(amine)2O2 site. The CuII and MII ions are bridged by a phenolic oxygen and an exogenous chloride ion. The CuII2NiII2 complex has a defect double-cubane structure. Cryomagnetic studies for the CuII2CoII2 complex indicate an antiferromagnetic spin-exchange interaction within each dinuclear CuIICoII unit (J = -9.5 cm-1 based on H = -2JSCuSCo). The CuII2NiII2 complex shows a weak antiferromagnetic interaction between the adjacent CuII and NiII ions (-3.5 cm-1) and a weak ferromagnetic interaction between the two NiII ions (+2.0 cm-1.

AB - The reaction of N,N′-dimethyl-N,N′-ethylenebis (5-bromo-3-formyl-2-hydroxybenzylaminato)copper(II) with ethylenediamine in aqueous DMF with excess perchloric acid resulted in the [2:2] cyclic condensation of the constituents, providing the dinuclear CuII complex [Cu2(H2R)](ClO4)2. It crystallizes in the monoclinic space group P21/c, with a = 19.603(3) Å, b = 13.370(2) Å, c = 21.072(3) Å, β = 98.87(1)° V = 5456(1) Å3, and Z = 4. The ligand R4- has two N(amine)2O2 and two N(imine)2O2 metal-binding sites sharing two phenolic oxygens, and [Cu2(H2R)](ClO4)2 has the two CuII ions in the N(imine)2O2 sites and two protons in the N(amine)2O2 sites. [Cu2(H2R)](ClO4)2 was converted by neutralization into [Cu2(R)], from which mixed-metal CuII2MII2 complexes [Cu2M2(R)Cl4] (M = CoII, NiII, ZnII) were derived. [Cu2Co2 (R)Cl4]·2CHCl3·H2O crystallizes in the monoclinic space group C2/c, with a = 32.514(3) Å, b = 12.246(3) Å, c = 19.827(2) Å, β = 126.082(1)° V = 6380(1) Å3, and Z = 4. [Cu2Zn2(R)Cl4] ·2CHCl3·H2O crystallizes in the monoclinic space group C2/c, with a = 32.53(1) Å, b = 12.242(2) Å, c = 19.729(9) Å, β = 126.03(3)°, V = 6354(4) Å3, and Z = 4. The two complexes are isotructural and have a dimer-of-dimers structure with two separated CuIIMII units. In each dinuclear unit, the CuII is bound to the N(imine)2O2 site and the MII is bonded to a phenolic oxygen and two nitrogens of the N(amine)2O2 site. The CuII and MII ions are bridged by a phenolic oxygen and an exogenous chloride ion. The CuII2NiII2 complex has a defect double-cubane structure. Cryomagnetic studies for the CuII2CoII2 complex indicate an antiferromagnetic spin-exchange interaction within each dinuclear CuIICoII unit (J = -9.5 cm-1 based on H = -2JSCuSCo). The CuII2NiII2 complex shows a weak antiferromagnetic interaction between the adjacent CuII and NiII ions (-3.5 cm-1) and a weak ferromagnetic interaction between the two NiII ions (+2.0 cm-1.

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