Add time:07/22/2019         Source:sciencedirect.com

The solid state thermal behaviors of (+)589-[Cr(en)3]Cl3·2H2O (no catalyst) and (+)589-[Cr(en)3]Cl3·1.7H2O (containing NH4Cl as a catalyst) have been investigated using DSC, TG and isothermal techniques. In contrast to the case of (+)589-[Cr(en)3](SCN)3, the present thermal reactions include dehydration, racemization and deamination reaction steps which can be observed separately. The reaction parameters for the dehydration, racemization and deamination reactions of the title complex have been determined. It was found that the activation energies for racemization reaction derived from the DSC measurements, 32.1 kcal/mol, and from the isothermal techniques, 33 kcal/mol, are quite similar for (+)589-[Cr(en)3]Cl3·1.7H2O. These values are larger than the corresponding value, 21.6 kcal/mol, for (+)589-[Cr(en)3]Cl3·2H2O. The deamination reaction of the present optically active complex proceeds a two step process to produce racemic cis-dichlorobis-(ethylenediamine)chromium(III) chloride. Moreover, the corresponding racemic complex, (±)-[Cr(en)3]Cl3·3H2O, was studied in the same condition. The temperature at which the deamination reaction of the optically active complex begins is considerably lower than that of the racemic complex. The reported crystal structures of both complexes have been compared minutely and the origin of this difference in the deamination reaction has been discussed.

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