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Binuclear cobalt(II/II) and cobalt(II/III) chelates with O2N2 ligands: synthesis, structure and magnetic studies

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Abstract

The title complexes \( [{\text{Co}}^{\text{II}}_{2} {\text{L}}^{ 1}_{2} ] \) and \( [{\text{Co}}^{\text{II}} {\text{Co}}^{\text{III}} ( {\text{OAc)L}}^{ 2}_{2} ] \) have been synthesized in excellent yields by reacting Co(OAc)2·4H2O with H2L1 and H2L2, respectively, in acetonitrile solution. Here, [L1]2− and [L2]2− are the deprotonated forms of N,N-bis(2-hydroxybenzyl)-N′,N′-dimethylethylenediamine and N,N-bis(2-hydroxybenzyl)-2-picolylamine, respectively. The crystal structures of \( [{\text{Co}}^{\text{II}}_{2} {\text{L}}^{ 1}_{2} ] \) and \( [{\text{Co}}^{\text{II}} {\text{Co}}^{\text{III}} ( {\text{OAc)L}}^{ 2}_{2} ]{\cdot}{\text{H}}_{ 2} {\text{O}}{\cdot}{\text{CH}}_{ 2} {\text{Cl}}_{ 2} \) were determined by x-ray crystallography. In \( [{\text{Co}}^{\text{II}}_{2} {\text{L}}^{ 1}_{2} ] \), each cobalt atom has distorted trigonal bipyramid geometry, while in \( [{\text{Co}}^{\text{II}} {\text{Co}}^{\text{III}} ( {\text{OAc)L}}^{ 2}_{2} ] \), each cobalt atom has distorted octahedral geometry. Variable temperature magnetic moment measurements show weak antiferromagnetic interaction in \( [{\text{Co}}^{\text{II}}_{2} {\text{L}}^{ 1}_{2} ] \). The magnetic characterization for \( [{\text{Co}}^{\text{II}} {\text{Co}}^{\text{III}} ( {\text{OAc)L}}^{ 2}_{2} ] \) is in agreement with the presence of Co(II) and Co(III) centers.

Graphical Abstract

The title complexes \( [{\text{Co}}^{\text{II}}_{2} {\text{L}}^{ 1}_{2} ] \) and \( \left[ {\left( {{\text{Co}}^{\text{II}} {\text{Co}}^{\text{III}} } \right){\text{L}}^{ 2}_{2} } \right] \) have been synthesized in excellent yields by reacting Co(OAc)2·4H2O with dianionic N2O2 coordinating ligands. In complex 1, each cobalt atom has distorted trigonal bipyramid geometry, while in complex 2, each cobalt atom has distorted octahedral geometry. Variable temperature magnetic moment measurements show weak antiferromagnetic interaction in complex 1. The magnetic characterization for complex 2 is in agreement with the presence of Co(II) and Co(III) centers.

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Acknowledgments

Financial supports from Council of Scientific and Industrial Research, New Delhi, India. And Department of Science and Technology, New Delhi, India. The University Grant Commission, New Delhi is greatly acknowledged. We are also thankful to School of Chemistry, Hyderabad University, India, and Department of Chemistry, Indian Institute of Technology, Guwahati, India for the data collection on the CCD facility setup. The author also acknowledges SAIF, IIT Bombay, India for EPR measurements.

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Correspondence to Kajal Krishna Rajak.

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Singh, R., Banerjee, A., Gordon, Y. et al. Binuclear cobalt(II/II) and cobalt(II/III) chelates with O2N2 ligands: synthesis, structure and magnetic studies. Transition Met Chem 34, 689–694 (2009). https://doi.org/10.1007/s11243-009-9249-1

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Keywords

  • Electron Paramagnetic Resonance
  • Cobalt Atom
  • Tcne
  • Trigonal Bipyramid Geometry
  • Variable Temperature Magnetic Susceptibility