Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

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


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.

This is a preview of subscription content, log in to check access.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Scheme 1


  1. 1.

    Shi H, Xu X, Ding X, Liu X, Li L, Kang W (2009) Anal Biochem 387:178

  2. 2.

    Xu X, Shi H, Ma L, Kang W, Li S (2010) Luminescence (in press)

  3. 3.

    Shi H, Shen S, Sun H, Liu Z, Li L (2007) J Inorg Biochem 101:165

  4. 4.

    Shen S, Shi H, Sun H (2007) Int J Chem Kinet 39:440

  5. 5.

    Shi H, Kang W, Shen S (2009) Transit Met Chem 34:91

  6. 6.

    Sun H, Shi H, Shen S, Kang W, Guo Z (2008) Chin J Chem 26:615

  7. 7.

    Shi H, Liu S, Shen S, Huo S, Kang W (2009) Transit Met Chem 34:821

  8. 8.

    Shen S, Du R, Shi H, Hao Z, Peng S (2009) J Hebei Univ 29:311 (Natural Science Edition)

  9. 9.

    Sinsheimer JE, Kauhnelian AM (1966) J Pharm Sci 55:1240

  10. 10.

    Alm S, Jonson S, Karlsson H, Sundholm EG (1983) J Chromatogr 254:179

  11. 11.

    Römhild W, Krause D, Bartels H, Ghanem A, Schöning R, Wittig H (2003) Foren Sci Int 33:101

  12. 12.

    Blikungeri A, Pelletier M, monnier D (1977) Inorg Chim Acta 22:7

  13. 13.

    Blikungeri A, Pelletier M (1978) Inorg Chim Acta 29:141

  14. 14.

    Clamp JR, Hough L (1965) Biochem J 94:17

  15. 15.

    Shi TS, He JT, Ding TH, Wang AZ (1991) Int J Chem Kinet 23:815

Download references


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).

Author information

Correspondence to Shigang Shen.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

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

Download citation


  • DNPH
  • KIO4
  • Mechanistic Picture
  • Mephenesin
  • Present Reaction System