Synergistic Effect of [Ru(III) + Ir(III)] in N-Bromosuccinimide Reaction with Certain Aliphatic Ketones: A Kinetic Study

P. Giridhar Reddy, K. Ramesh, S. Shylaja, K. C. Rajanna, S. Kandlikar
2012 Advances in Physical Chemistry  
Dramatic rate enhancements have been observed in the oxidation of acetone (MMK), ethyl methyl ketone (EMK), and isobutyl methyl ketone (IBMK) by N-bromosuccinimide (NBS) in the presence of a mixture of metal ions [Ru(III) + Ir(III)]. The rate of oxidation in the the [Ru(III) + Ir(III)] system is much faster than either in the Ru(III) or in Ir(III) catalyzed system. The order in [NBS] was found to be zero both in catalyzed as well as uncatalyzed reactions. However, the order in [ketone] changed
more » ... n [ketone] changed from unity to a fractional one in metal ion catalyzed systems. On the basis of kinetic features, the most plausible mechanism involving the oxidation of [Ir(III)-ketone] by Ru(III) to give [Ir(V)-ketone] and Ru(I) in the rate limiting step is proposed. Ru(I) thus formed is oxidized by NBS to Ru(III) in a fast step is discussed and individual rate parameters were evaluated.
doi:10.1155/2012/292908 fatcat:k4u2atnaercw5e33csanv7jpxy