Issue 15, 1996

Synthesis, structure and spectroscopic studies on hydroxo-bridged heterotrinuclear complexes of cobalt(III) with ethane-1,2-diamine and ammonia as terminal ligands

Abstract

Hydroxo-bridged homo- and hetero-trinuclear cobalt(III) complexes of the type [MII(H2O)2{(OH)2CoIII(N4)}2]X2·nH2O [MII= a divalent metal ion such as CoII, NiII or ZnII; N4=(en)2(en = ethane-1,2-diamine) or (NH3)4; X = SO4 or (ClO4)2; n= 3 or 5] have been prepared and spectroscopically characterized. The structure of [Cu{(OH)2Co(en)2}2][SO4]2·2H2O 1 has been determined. The geometry around copper atom is a pseudo-square-based pyramid, with the basal sites occupied by four bridging hydroxide oxygens and the apical site is occupied by a weakly co-ordinated sulfate anion [Cu–O 2.516(4)Å]. The hydroxo groups bridge pairs of cobalt(III) ions which are in near-octahedral environments. The ethylenediamine chelate rings have the twist conformation. In the crystal structure of [Cu{(OH)2Co(en)2}2][ClO4]4·2H2O 2 the perchlorate ion is not co-ordinated and the en ligands have ‘envelope’ conformations. The sulfate ion in [Cu{(OH)2Co(NH3)4}2][SO4]2·4H2O 3 is not co-ordinated to the central copper ion. Electronic, infrared and variable-temperature EPR spectral data are discussed.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1996, 3179-3184

Synthesis, structure and spectroscopic studies on hydroxo-bridged heterotrinuclear complexes of cobalt(III) with ethane-1,2-diamine and ammonia as terminal ligands

K. V. P. M. Shafi, M. Nethaji and D. N. Sathyanarayana, J. Chem. Soc., Dalton Trans., 1996, 3179 DOI: 10.1039/DT9960003179

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