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

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

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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) 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

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Keywords

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

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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