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Kinetics and mechanism of oxidation of N-methylethylamine by bis(hydrogenperiodato)argentate(III) complex anion

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Abstract

Oxidation of N-methylethylamine by bis(hydrogenperiodato)argentate(III) ([Ag(HIO6)2]5−) in alkaline medium results in demethylation, giving rise to formaldehyde and ethylamine as the oxidation products. The oxidation kinetics has been followed spectrophotometrically in the temperature range of 20.0–35.0 °C, and shows an overall second-order character: being first-order with respect to both Ag(III) and N-methylethylamine. The observed second-order rate constants k′ increase with increasing [OH−] of the reaction medium, but decrease with increasing the total concentration of periodate. An empirical rate expression for k′ has been derived as: k′ = (k a + k b[OH−])K 1/{f([OH−])[IO4 −]tot + K 1}, where k a and k b are rate parameters, and K 1 is an equilibrium constant. These parameters have been evaluated at all the temperatures studied, enabling calculation of activation parameters. A reaction mechanism is suggested to involve two pre-equilibria, leading to formation of an intermediate Ag(III) complex, namely [Ag(HIO6)(OH)(MeNHEt)]2−. In the subsequent rate-determining steps, this intermediate undergoes inner-sphere electron transfer from the coordinated amine to the metal center via two distinct routes, one of which is spontaneous while the other is mediated by a hydroxide ion.

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Acknowledgments

This work was carried out under the guidance of Dr. Tiesheng Shi and was financially supported in part by a grant from the Natural Science Foundation of Hebei Province (B2006000962).

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Authors and Affiliations

  1. College of Chemistry and Environmental Science, Hebei University, 071002, Baoding, Hebei, People’s Republic of China

    Yukun Guo, Shuying Huo & Shigang Shen

  2. School of Public Health, Hebei Medical University, 050017, Shijiazhuang, Hebei, People’s Republic of China

    Hongmei Shi

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  1. Yukun Guo
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  2. Hongmei Shi
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  3. Shuying Huo
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  4. Shigang Shen
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Correspondence to Shigang Shen.

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Guo, Y., Shi, H., Huo, S. et al. Kinetics and mechanism of oxidation of N-methylethylamine by bis(hydrogenperiodato)argentate(III) complex anion. Transition Met Chem 36, 59–64 (2011). https://doi.org/10.1007/s11243-010-9434-2

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  • DOI: https://doi.org/10.1007/s11243-010-9434-2

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