Some oxalato–amine complexes of nickel(II), copper(II), and zinc(II)

Abstract

Preparations of the compounds [{Ni(1,3-pn)₂}₂C₂O₄](ClO₄)₂,H₂O, [{Ni(dpt)H₂O}₂C₂O₄](ClO₄)₂, [{Cu(dien)}₂C₂O₄](ClO₄)₂(and hydrate), [{Cu(dpt)}₂C₂O₄](ClO₄)₂, [{Zn(en)₂}₂C₂O₄](ClO₄)₂, [{Zn(dpt)}₂C₂O₄](ClO₄)₂, and [{Zn(trien)}₂C₂O₄](ClO₄)₂, considered to have dimeric structures with bridging bichelate oxalate ions, are described. The pairs of compounds [{M(en)₂}₂C₂O₄](ClO₄)₂ and [{M(trien)}₂C₂O₄](ClO₄)₂[M = Ni(II) or Zn(II)] are isostructural, whereas the pair [{M(dpt)}₂C₂O₄](ClO₄)₂[M = Cu(II) or Zn(II)] are not isostructural. The racemic isomer of the cyclic tetramine 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-azacyclotetradecane forms an analogous compound, [{Ni(tet b)}₂C₂O₄](ClO₄)₂, whereas the meso-isomer forms only a simple oxalate, Ni(tet a)C₂O₄, and its trihydrate, considered to have polymeric structures with bridging, bi-unidentate oxalate ions. The compounds [Zn(1,3-pn)₂](ClO₄)₂ and [Zn₃(trien)₄](ClO₄)₆ were also prepared. Infrared spectra and magnetic susceptibilities (µ_eff∼ 3 B.M. for the nickel compounds and ∼1·8 B.M. for the copper compounds) are reported (en = diaminoethane; 1,3-pn = 1,3-diaminopropane; dien = diethylenetriamine; dpt = dipropylenetriamine; trien = triethylenetetramine).