594-73-0Relevant academic research and scientific papers
Electron Transfer Reactions in Organic Chemistry. XIII. The Reaction between Carbon Teterabromide and the Heteropoly Blues Co(II)W12O407- and Co(II)W12O408-. A Kinetic and Product Study
Eberson, Lennart,Ekstroem, Mikael
, p. 101 - 112 (2007/10/02)
The reaction between carbon tetrabromide and Co(II)W12O407- was investigated at 20 deg C in CH3CN/H2O (64/36 v/v) buffered at pH ca.7.It was found to be first-order in both substrate and reagent, the rate determining step being an outer-sphere electron transfer reaction.The rate constant was determined to be 1.1 +/- 0.3 M-1 s-1.The only products found were CHBr3 (77percent) and C2Br6(1percent).Product studies in CH3CN/D2O showed that almost all of the tribromomethyl radical formed in the first step was further reduced to the corresponding anion.The rate constant for this reaction was estimated to be 106 M-1 s-1.The effect of inert salts on the overall reaction rate was also investigated.Tetraalkylammonium salts were found to augment the rate while alkali metal ions lowered it, which is the opposite of results with heteropoly ions as oxidants.The reaction between CBr4 and Co(II)W12O408- was first order in heteropoly blue and if it was assumed it was first-order in CBr4 also, the rate constant could be calculated to be 4.3 M-1 s-1.
Electron Transfer Reactions in Organic Chemistry. XI. The Reaction between Carbon Tetrabromide and the Cage Complex 2+. A Kinetic and Product Study
Eberson, Lennart,Ekstroem, Mikael
, p. 41 - 49 (2007/10/02)
A kinetic and product study of the reaction between CBr4 and the cage complex 2+ in CH3CN/H2O at 20 deg C has been performed.The reaction was found to be first order in both CBr4 and 2+, the only products found being CHBr3 and C2Br6.The mechanism is discussed and suggested to be an outer-sphere electron transfer mechanism, with a rate constant for the rate determining electron transfer step kET = 0.020 M-1 s-1 (CH3CN/H2O ; 36 mM, 3.6 mM and 9.1 mM).The possibility that the complexation c hemistry of CBr4 might influence the reaction is critically considered.
