Kinetics of the ruthenium(III) catalyzed oxidation of amides by sodium N-bromotoluenesulfonamide in hydrochloric acid solution

Ananda, S. and Jagadeesha, M. B. and Rai, K. M. Lokanatha and Made Gowda, N. M. (1999) Kinetics of the ruthenium(III) catalyzed oxidation of amides by sodium N-bromotoluenesulfonamide in hydrochloric acid solution. Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 29 (1). pp. 1-21. ISSN 0094-5714

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Abstract

The kinetics of Ru(III) catalyzed oxidations of urea, methylurea and ethylurea by sodium N-bromo-p-toluenesulfonamide, also known as bromamine-T (BAT), in HCl solution has been studied at 30 degrees C. The reaction rate shows a first-order dependence each on BAT], amide] and Ru(III)I and fractional-order on H+]. Additions of halide ions and the reaction product of BAT (p-toluenesulfonamide) and the variation of ionic strength and dielectric constant of the medium do not have any significant effect on the reaction rate. Activation parameters have been evaluated. A Taft linear free energy relationship is observed for the reaction, with rho*= -0.64 and -2.95 and delta = -0.25, indicating that electron donating groups enhance the rate. An isokinetic relationship is observed with beta = 391 K indicating that enthalpy factors control the rate. The existence of the relationship has been supported by the Exner criterion. The protonation constant of monobromamine-T calculated from a plot of 1/k' versus 1/H+] is 29.15. Mechanisms consistent with the observed kinetic data have been proposed.

Item Type:	Article
Subjects:	C Chemical Science > Chemistry
Divisions:	Department of > Chemistry
Depositing User:	Users 23 not found.
Date Deposited:	12 Jun 2021 07:15
Last Modified:	06 Jul 2022 07:54
URI:	http://eprints.uni-mysore.ac.in/id/eprint/16857

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