非水溶媒中の銅(2)錯体の電極反応--サリチルアルデヒドおよび類縁化合物の銅錯体のポ-ラログラフ的挙動

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Electrochemical behaviours of several copper (II) complexes with salicylaldehyde and related compounds in non aqueous solvents are studied. Both Cu(C7H5O2)2 and Cu(C7H6NO2)2 give diffusion controlled polarographic waves of irreversible two electron process in DMF. Cu(OC6H4CHNOH)2, gives two diftussion controlled irreversible reduction waves. The wave height depends on both solvents and pHc of the solution. The height of the first wave increases with decreasing pHc of the solution, while the height of the second wave increases with increasing pHc of the solution. The sum of the both wave heights remains unchanged. These two waves correspond to two different complex species in the solution. Species A, corresponding to the first wave predominates over the another species in the presence of weak acids such as salicylaldoxime and species B, corresponding to the second wave predominates in the presence of Et4N+ salt of salicylaldoxime. An equilibrium between these two species, A and B, depends on solvent. In DMF, species A predominates while in both DMSO and HEMPA, species B predominates. Copper (II)-aldoxime complex is a single planar complex stabilized by intramolecular hydrogen bonds in both non polar solvents and solid state. In polar solvents, Copper (II)-aldoxime complex seems to exist as a mixture of two species, an equilibrium of which depends on a basicity of a solvent.
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