Derivatographic Studies on Transition Metal Complexes. XVII. Solid-phase Deaquation-anation of Some Optically Active Aqua—cobalt(III) Complexes

Stereochemical changes involved in the solid-phase deaquation-anation of the following optically active aqua-cobalt(III) complexes were investigated: (+)546-cis-[Co(H2O)2en2]X3·2H2O (X=Cl or Br), (+)589-cis-α[CoCl(H2O)en2]Cla·H2O, (−)589-cis-[CoCl(H2O)en2]Br2·H2O, (+)589-α-[CoCl(H2O)trien]Cl2·H2O and (+)589-α-[CoCl(H2O)trien]Br2·2H2O, where en and trien denote ethylenediamine and triethylenetetramine, respectively. Thermal deaquation-anation processes for each complex were observed with a derivatograph, polarimeter, and UV and CD spectrophotometers. cis-[Co(H2O)2en2]Cl3·2H2O was converted into cis-[CoCl(H2O)en2]Cl2 at first and then cis-[CoCl2en2]Cl; the stereochemical changes during the first step and the second step were found to be retention and racemization, respectively. In contrast, a predominant stereochemical change involved in the deaquation-anation of cis-[Co(H20)2en2]Br3·2H2O was cis-to-trans isomerization. The deaquation-anation of cis-[CoCl(H2O)en2]Cl2·H2O and cis-[CoCl(H2O)en2]Br2·2H2O was f...

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