Iminoquinone coordination to copper(I) in the [Cu(PhenoxBQ) (μ-Cl)]2 dimer

G. Speier, Jozsef Csihony, Anne M. Whalen, Cortlandt G. Pierpont

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

The addition of 2,4,6,8-tetra-tert-butylphenoxazin-1-one (PhenoxBQ) to an acetonitrile solution of CuCl leads to the formation of the [Cu(PhenoxBQ) (μ-Cl)]2 dimer. Structural characterization on crystals of the dimer obtained by recrystallization from dichloromethane (triclinic, P1̄ , a=10.559(1), b=11.914(3), c=13.530(4) Å, a=85.55(2), β=74.57(2), γ=75.52(2)°, V=1588.5(6) Å3, Z=1, R=0.079) has shown that the coordination geometry about the metals is tetrahedral. The Cu-Cu separation of 2.826(1) Å and the Cu-Cl lengths of 2.215(3) and 2.289(2) Å are unusually short among chloro-bridged Cu(I) dimers. Addition of PhenoxBQ to CuCl2 results in the formation of [Cu(PhenoxBQ)Cl2]2, also formulated as a dimer on the basis of its magnetic and electrochemical properties. Both dimers show the four-membered redox series that appears characteristically for complexes containing two PhenoxBQ or PhenoxSQ ligands. In the case of [CuI(PhenoxBQ)Cl]2 an oxidation at +1.043 V (versus NHE) has been assigned as the Cu(I)/Cu(II) couple associated with oxidation of one metal ion of the dimer.

Original languageEnglish
Pages (from-to)1-5
Number of pages5
JournalInorganica Chimica Acta
Volume245
Issue number1
DOIs
Publication statusPublished - Apr 1 1996

Fingerprint

Dimers
Copper
Metals
dimers
copper
Methylene Chloride
Oxidation-Reduction
Ions
Ligands
Oxidation
oxidation
Dichloromethane
Acetonitrile
Electrochemical properties
acetonitrile
Metal ions
iminoquinone
metal ions
Magnetic properties
magnetic properties

Keywords

  • Copper complexes
  • Crystal structures
  • Dinuclear complexes
  • Iminoquinone complexes

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Iminoquinone coordination to copper(I) in the [Cu(PhenoxBQ) (μ-Cl)]2 dimer. / Speier, G.; Csihony, Jozsef; Whalen, Anne M.; Pierpont, Cortlandt G.

In: Inorganica Chimica Acta, Vol. 245, No. 1, 01.04.1996, p. 1-5.

Research output: Contribution to journalArticle

Speier, G. ; Csihony, Jozsef ; Whalen, Anne M. ; Pierpont, Cortlandt G. / Iminoquinone coordination to copper(I) in the [Cu(PhenoxBQ) (μ-Cl)]2 dimer. In: Inorganica Chimica Acta. 1996 ; Vol. 245, No. 1. pp. 1-5.
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abstract = "The addition of 2,4,6,8-tetra-tert-butylphenoxazin-1-one (PhenoxBQ) to an acetonitrile solution of CuCl leads to the formation of the [Cu(PhenoxBQ) (μ-Cl)]2 dimer. Structural characterization on crystals of the dimer obtained by recrystallization from dichloromethane (triclinic, P1̄ , a=10.559(1), b=11.914(3), c=13.530(4) {\AA}, a=85.55(2), β=74.57(2), γ=75.52(2)°, V=1588.5(6) {\AA}3, Z=1, R=0.079) has shown that the coordination geometry about the metals is tetrahedral. The Cu-Cu separation of 2.826(1) {\AA} and the Cu-Cl lengths of 2.215(3) and 2.289(2) {\AA} are unusually short among chloro-bridged Cu(I) dimers. Addition of PhenoxBQ to CuCl2 results in the formation of [Cu(PhenoxBQ)Cl2]2, also formulated as a dimer on the basis of its magnetic and electrochemical properties. Both dimers show the four-membered redox series that appears characteristically for complexes containing two PhenoxBQ or PhenoxSQ ligands. In the case of [CuI(PhenoxBQ)Cl]2 an oxidation at +1.043 V (versus NHE) has been assigned as the Cu(I)/Cu(II) couple associated with oxidation of one metal ion of the dimer.",
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N2 - The addition of 2,4,6,8-tetra-tert-butylphenoxazin-1-one (PhenoxBQ) to an acetonitrile solution of CuCl leads to the formation of the [Cu(PhenoxBQ) (μ-Cl)]2 dimer. Structural characterization on crystals of the dimer obtained by recrystallization from dichloromethane (triclinic, P1̄ , a=10.559(1), b=11.914(3), c=13.530(4) Å, a=85.55(2), β=74.57(2), γ=75.52(2)°, V=1588.5(6) Å3, Z=1, R=0.079) has shown that the coordination geometry about the metals is tetrahedral. The Cu-Cu separation of 2.826(1) Å and the Cu-Cl lengths of 2.215(3) and 2.289(2) Å are unusually short among chloro-bridged Cu(I) dimers. Addition of PhenoxBQ to CuCl2 results in the formation of [Cu(PhenoxBQ)Cl2]2, also formulated as a dimer on the basis of its magnetic and electrochemical properties. Both dimers show the four-membered redox series that appears characteristically for complexes containing two PhenoxBQ or PhenoxSQ ligands. In the case of [CuI(PhenoxBQ)Cl]2 an oxidation at +1.043 V (versus NHE) has been assigned as the Cu(I)/Cu(II) couple associated with oxidation of one metal ion of the dimer.

AB - The addition of 2,4,6,8-tetra-tert-butylphenoxazin-1-one (PhenoxBQ) to an acetonitrile solution of CuCl leads to the formation of the [Cu(PhenoxBQ) (μ-Cl)]2 dimer. Structural characterization on crystals of the dimer obtained by recrystallization from dichloromethane (triclinic, P1̄ , a=10.559(1), b=11.914(3), c=13.530(4) Å, a=85.55(2), β=74.57(2), γ=75.52(2)°, V=1588.5(6) Å3, Z=1, R=0.079) has shown that the coordination geometry about the metals is tetrahedral. The Cu-Cu separation of 2.826(1) Å and the Cu-Cl lengths of 2.215(3) and 2.289(2) Å are unusually short among chloro-bridged Cu(I) dimers. Addition of PhenoxBQ to CuCl2 results in the formation of [Cu(PhenoxBQ)Cl2]2, also formulated as a dimer on the basis of its magnetic and electrochemical properties. Both dimers show the four-membered redox series that appears characteristically for complexes containing two PhenoxBQ or PhenoxSQ ligands. In the case of [CuI(PhenoxBQ)Cl]2 an oxidation at +1.043 V (versus NHE) has been assigned as the Cu(I)/Cu(II) couple associated with oxidation of one metal ion of the dimer.

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