Kinetics and Mechanism for Oxidation of L‐Proline by Bis(hydrogen periodato)argentate(III) Complex Anion

Abstract

Oxidation of L-proline by bis(hydrogen periodato)argentate(III) complex anion, [Ag(HIO 6 complex. Both Ag(III) complexes are reduced parallelly by the fully deprotonated form of proline in rate-determining steps (described by k 1 for the former Ag(III) and k 2 for the latter one). The determined rate constants and their associated activation parameters are k 1 (25

Do oxidations of α-diols by bis(hydrogenperiodato)argentate(III) proceed according to different rate laws?

“…7 is derived in terms of the total concentration of Ag(III) complex if K 2 [a-diol] (1. [1][2][3]. Therefore, …”

“…By considering the kinetic characters in this study and in our recent studies on the Ag(III) oxidations [1][2][3], a reaction mechanism for oxidation of a-diols by the Ag(III) complex is tentatively suggested as described in Scheme 1. Rate Eq.…”

“…However, the reported rate laws and the proposed mechanisms were markedly different in these two studies. In view of our own previous studies and comments on the Ag(III) complex [1][2][3], we decided to carry out a kinetic study on the oxidations of a-diols (ethylene glycol, 1,2-propanediol and 1,2-butanediol) by [Ag(HIO 6 ) 2 ] 5-under conditions similar to those used by Shan et al In this article, we report our experimental findings.…”

“…Our purposes are (a) to elucidate the reaction mechanisms, (b) to compare the mechanistic similarities and differences, and (c) to find out how the substrate structures affect the rate laws and reaction mechanisms [1][2][3]. In a recent study [2], we addressed in detail the correct structure of the Ag(III) complex and the reactive species and highlighted some doubtful assignments to the Ag(III) complex by other researchers (cf.…”

“…In the last few years, we have been focusing on the interactions between bis(hydrogenperiodato)argentate(III) complex anion, [Ag(HIO 6 ) 2 ] 5-, and biologically and biomedically important molecules [1][2][3]. Our purposes are (a) to elucidate the reaction mechanisms, (b) to compare the mechanistic similarities and differences, and (c) to find out how the substrate structures affect the rate laws and reaction mechanisms [1][2][3].…”