EPR study on ligand-exchange reaction between bis(diethyldiselenocarbamato)copper(II) and some bis(acetylacetonato)copper(II) complexes

Abstract

The paper is a study on the formation and properties of mixed-chelate copper(II) complexes, in which one ligand is strongly covalently bound diselenocarbamate (dsc), and the other belongs to a series of differently substituted acetylacetonates (acac), all forming weak covalent bonds. Thenoyltrifluoro- and trifluoro- substituted acetylacetonates only partly form mixed-chelate complexes, stable in toluene, benzene or dichloromethane, but gradually decomposing in chloroform or carbontetrachloride by analogy with Cu(Et 2dsc) 2 behavior in these solvents. Hexafluoro-acetylacetonato copper(II) completely turns into a mixed-chelate Cu(dsc)(hfacac), which remains unchanged for more than 8 months of monitoring in all solvents used. The stability of Cu(dsc)(hfacac) is attributed to the reduced remaining negative charge on selenium atom embarrassing the formation of weak D–A complex with haloalkanes. The obtained EPR parameters suggest significant lowering of the contribution of the 4s AO of copper(II) in the mixed-chelate complexes. It is shown that Cu(acac) 2 does not react with Cu(Et 2dsc) 2.