Kinetic studies of fast equilibrium by means of high-performance liquid chromatography. III. Ternary complex formation between Ni(II) diethyldithiocarbamate and other unlike Ni(II) chelates.
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The labile ternary complex formation (MA<SUB>2</SUB>+MB<SUB>2</SUB>\rightleftharpoons2MAB with <I>K</I>=[MAB]<SUP>2</SUP>/([MA<SUB>2</SUB>][MB<SUB>2</SUB>])) between Ni(II) diethyldithiocarbamate(MA<SUB>2</SUB>) and other several Ni(II) chelates(MB<SUB>2</SUB>) was investigated by high-performance liquid chromatography; two solutions of MA<SUB>2</SUB> and MB<SUB>2</SUB> were mixed and equilibrated. The tendency to form a ternary complex is summarized as follows: (1) no ternary complex formation takes place (B=dimethylglyoxime and 1-(2-pyridylazo)-2-naphthol), for which high structural stability of binary complex MB<SUB>2</SUB> is responsible; (2) the ternary complex formation is controlled statistically (<I>K</I>=4.0), suggesting the absence of any factor to stabilize or unstabilize the ternary complex (B=<I>N</I>,<I>N</I>-disubstituted dithiocarbamates and <I>N</I>-monosubstituted dithiocarbamates); (3) the ternary complex formation is favored (<I>K</I>>4.0) (B=xanthates); and (4) all initial binary complexes are converted into a very stable species which is possibly a ternary complex (B=dithizone). Kinetic characteristics of these ternary complex formations are examined.
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