Czasopismo | RUDY I METALE NIEŻELAZNE | Rocznik 2016 - zeszyt 10

Kinetics of the Reaction of cis - and trans-PtCl4(NH3)2 Complexes in Aqueous Solution, in the Presence of Ethanol

10.15199/67.2016.10.4

nr katalogowy: 101821
10.15199/67.2016.10.4

In this work the kinetic data for the reactions of cis- and trans-PtCl4(NH3)2 complexes with ethanol have been determined. Obtained values of the rate constants determined for different conditions of reactants concentration as well as different temperature indicate that in aqueous solution with pH = 12 the reaction is relatively slow and leads to the cis- and trans-PtCl2(NH3)2 species formation, respectively. Using obtained kinetic results, supported with DFT calculations, the possible mechanism of electron transfer involving the chloride ligand-ethanol bridge formation has been suggested. It was found that the values of enthalpy and entropy of activation correlate well with the difference between the rate constants of both reacting pairs as well as with the difference between HOMO and LUMO energy levels of reagents. From the obtained results, the parallel paths of the cis- and trans-PtCl4(NH3)2 reactions, i.e. reduction and hydrolysis of platinum(IV) complexes, were also suggested. Keywords: kinetics, mechanism, rate law, cis-PtCl4(NH3)2, trans-PtCl4(NH3)2, platinum(IV) KINETYKA REAKCJI KOMPLEKSÓW cis- I trans-PtCl4 (NH3)2 W ROZTWORZE WODNYM, W OBECNOŚCI ETANOLU W artykule przedstawiono dane kinetyczne reakcji kompleksów cis- i trans-PtCl4(NH3)2 z etanolem. Wartości stałych szybkości wyznaczone w różnych warunkach stężenia reagentów oraz w różnych temperaturach wskazują, że w roztworach wodnych o pH = 12, reakcja jest względnie wolna i prowadzi to utworzenia odpowiednio cis- i trans-PtCl2(NH3)2. Używając otrzymanych danych kinetycznych oraz obliczeń DFT, zaproponowano możliwy mechanizm przekazania elektronu obejmujący utworzenie mostka: ligand chlorkowy-etanol. Wykazano, że wartości entalpii i entropii aktywacji dobrze korelują z różnicą pomiędzy stałymi szybkości reakcji obydwu par reagentów, jak również z różnicą pomiędzy poziomami energetycznymi HOMO i LUMO reagentów. Na podstawie otrzymanych danych oraz dyskusji wyników zaproponowano ró[...]

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