ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Crystal chemistry of complex Cu(II) compounds. I. Mechanism of substitution reactions

F.Hanic

Slovak Academy of Sciences, Bratislava

Abstract: Crystal chem. structure of [Cu₂(OAc)₄(H₂O₂)₂] (Van Niekerk and Schoening, CA 47, 6727g) and of [Cu₂(OAc)₄(C₅H₅N)₂] were studied and compared. Substitution in complex Cu(II) compds. occurs at the position of the weakest bound ligand. As soon as the substituting ligand (L₁) with a strong field enters the coordination sphere of Cu, the weakest bound ligand (L₂) is orientated trans to ligand L₁ and thus the trans position becomes most susceptible to substitution with addnl. ligand L₁. Cis derivs. form only with chelating ligands such as ethylenediamine or o-phenylenediamine. The crystal field of complex Cu(II) compds. should be regarded as a dynamic system, which changes by the effect of new substituents entering the crystal field so that a pair of weak bonds can be orientated in the direction of all 3 axes of the co.ovrddot.ordination octahedron.

Full paper in Portable Document Format: 151a14.pdf (in Slovak)

Chemical Papers 15 (1) 14–19 (1961)