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Oxidation of bis(dialkyldithiocarbamato)nickel(ii) with bromine and iodine

E. Beinrohr and J. Garaj

Department of Analytical Chemistry, Slovak Technical University, CS-812 37Bratislava

Abstract: The product of bis(dialkyldithiocarbamato)nickel(II) (Ni(II)L2) oxidation with bromine is the Ni(IV)L 3 Br complex (L is a dithiocarbamato ligand). Iodine oxidizes Ni(II)L2 to the complex Ni(III)L2l 3 in the nonpolar medium. The equilibrium constant of the reaction 2Ni(II)L2 + 3l2^2Ni(III)L 2 I 3 was determined spectrophotometrically. Its numerical value is (8.7 ± 1.5) x 10 5 for toluene and (5.0 ± 0.3) x 10 7 for chloroform, respectively. In the polar medium a final product of oxidation with iodine is the Ni(IV)L 3 I 3 complex which is thought to arise due to the disproportionation of the primarily formed Ni(III)L2l 3 complex.

Full paper in Portable Document Format: 393a303.pdf

Chemical Papers 39 (3) 303–315 (1985)