论文信息 - Derivatographic Studies on Transition Metal Complexes. VIII. Thermal Deaquation-Anation Reaction of cis -[CoX(H 2 O)N 4 ]Y 2 Type Complexes in Solid Phase

Derivatographic Studies on Transition Metal Complexes. VIII. Thermal Deaquation-Anation Reaction of cis -[CoX(H 2 O)N 4 ]Y 2 Type Complexes in Solid Phase

The deaquation-anation reaction of cis-[CoX(H2O)N4]Y2 type complexes, where X is chloride or bromide ion, N4 is tetraammine or bis(ethylenediamine), and Y is chloride, bromide or nitrate ion, was investigated by means of both derivatographic and isothermal methods. Some of these reactions were found to include the stereochemical changes, the structure of reaction products formed by deaquation-anation reaction being considerably affected by the counter ionic species: the chloride complexes, where Y=Cl, were deaquated with retention of cis-structure, whereas the bromide complexes, where Y=Br, underwent cis-to-trans stereochemical change. According to the isothermal measurement in the isomerization of cis-[CoCl(H2O)en2]Br2·H2O, cis-[CoCl(H2O)en2]-Br(NO3) and cis-[CoBr(H2O)en2]Br2·H2O, these rates were found to obey the first-order rate law and the activation energies, Ea, were obtained to be 38±5, 68±6 and 37±5 kcal mol−1 and the enthalpy changes, ΔH, 13.5±2.0, 7.5±2.0 and 13.3±2.0 kcal mol−1 for the respect...

E. Kyuno | Masatatsu Suzuki | R. Tsuchiya

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