A. Ohyoshi, S. Hiraki, T. Odate
1975
Citations
0
Influential Citations
9
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
The Kinetics of the thermal substitution reaction of hexaammineruthenium(III) halides and cis-dihalogenotetraammineruthenium(III) halides have been studied in the solid state. The reaction rates and kinetic parameters were determined for these two reactions; [Ru(NH3)6]X3→[RuX(NH3)5]X2+NH3, (X=Br, I) and cis-[RuX2(NH3)4]X→[RuX3(NH3)3]+NH3, (X=Cl, Br). The values of the rate constant, the activation energy, and the activation entropy were 2.10×10−5 s−1 (at 161°C), 23.3 kcal mol−1, and −29.3 e.u. for the hexaammine bromide, and 2.92×10−5s−1 (at 162 °C), 31.3 kcal mol−1, and −10.1 e.u. for the cis-dibromotetraammine bromide. The SN2 mechanism is more probable for the former reaction, while the SN1 mechanism is more probable for the latter reaction.