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Oxidation of d-Glucose by Silver(III) Periodate Complex in the Presence of Ru(III)/Os(VIII) as a Homogeneous Catalyst: A Comparative Mechanistic Study (Stopped Flow Technique)

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Abstract

The kinetics of the oxidation of ruthenium(III) (Ru(III)) and osmium(VIII) (Os(VIII)) catalyzed oxidation of d-glucose (d-Glu) by silver(III) periodate complex (DPA) in aqueous alkaline medium at 298 K and constant ionic strength 0.003 mol·dm−3 was studied spectrophotometrically. The reaction between d-Glu and DPA in alkaline medium exhibits 1:2 stoichiometry in both catalyzed reactions (d-Glu:DPA). The main products were identified as D-arabinonic acid and formic acid by spot tests, GC–MS spectra and chromatographic techniques. The reaction orders with respect to various species concentrations were determined. Also, the active species of catalyst and oxidant have been identified. Probable mechanisms were proposed. The activation parameters with respect to the slow step of the mechanism were computed and discussed and thermodynamic quantities were also calculated. It has been observed that the catalytic efficiency for the present reaction is in the order Os(VIII) > Ru(III).

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Scheme 1
Scheme 2
Scheme 3
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Acknowledgments

The authors thank the UGC, New Delhi, for the sanction of research grant (F. 36-136/2008 (SR) dated 27-03-2009).

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  1. P. G. Department of Studies in Chemistry, Karnatak University, Dharwad, 580003, India

    Sanjeevaraddi R. Sataraddi & Sharanappa T. Nandibewoor

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  1. Sanjeevaraddi R. Sataraddi
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Correspondence to Sharanappa T. Nandibewoor.

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Appendix

Appendix

According to Scheme 3:

$$ {\text{rate}} = k_{1} [{\text{C}}]\left[ {{\text{Ag}}({\text{H}}_{2} {\text{IO}}_{6} )({\text{H}}_{2} {\text{O}})} \right] = \frac{{k_{1} K_{1} K_{2} K_{3} \left[ {\text{DPA}} \right]\left[ {{\text{Ru}}({\text{III}})} \right]\left[ {{\text{OH}}^{ - } } \right]\left[ {\textsc{d}} {\text{-Glu}} \right]}}{{\left[ {\left[ {{\text{H}}_{3} {\text{IO}}_{6}^{2 - } } \right]} \right]}} $$
(A1)

The total concentration of DPA is given by (where t and f refer to total and free concentrations):

$$ \begin{aligned} \left[ {\text{DPA}} \right]_{\text{t}} & = \left[ {\text{DPA}} \right]_{\text{f}} + \left[ {{\text{Ag}}\left( {{\text{H}}_{3} {\text{IO}}_{6} } \right)\left( {{\text{H}}_{2} {\text{IO}}_{6} } \right)} \right]^{2 - } + \left[ {{\text{Ag}}\left( {{\text{H}}_{3} {\text{IO}}_{6} } \right)\left( {{\text{H}}_{2} {\text{O}}} \right)_{2} } \right] \\ & = \left[ {\text{DPA}} \right]_{\text{f}} \left\{ {\frac{{\left[ {{\text{H}}_{3} {\text{IO}}_{6}^{2 - } } \right] + K_{1} \left[ {{\text{OH}}^{ - } } \right]\left[ {{\text{H}}_{3} {\text{IO}}_{6}^{2 - } } \right] + K_{1} K_{2} \left[ {{\text{OH}}^{ - } } \right]}}{{\left[ {{\text{H}}_{3} {\text{IO}}_{6}^{2 - } } \right]}}} \right\} \\ \end{aligned} $$

Therefore:

$$ \left[ {\text{DPA}} \right]_{\text{f}} = \frac{{\left[ {\text{DPA}} \right]_{\text{t}} \left[ {{\text{H}}_{2} {\text{IO}}_{6}^{3 - } } \right]}}{{\left[ {{\text{H}}_{3} {\text{IO}}_{6}^{2 - } } \right] + K_{1} \left[ {{\text{OH}}^{ - } } \right]\left[ {{\text{H}}_{3} {\text{IO}}_{6}^{2 - } } \right] + K_{1} K_{2} \left[ {{\text{OH}}^{ - } } \right]}} $$
(A2)

In view of the low [DPA] and [\( {\text{H}}_{3} {\text{IO}}_{6}^{2 - } \)] values used:

$$ [{\text{OH}}^{ - } ]_{\text{t}} = [{\text{OH}}^{ - } ]_{\text{f}} $$
(A3)

Similarly:

$$ \left[ {\textsc{d}} {\text{-Glu}} \right]_{\text{t}} = \, \left[ {\textsc{d}} {\text{-Glu}} \right]_{\text{f}} + [{\text{C}}] = \left[ {\textsc{d}} {\text{-Glu}} \right]_{\text{f}} (1 \, + K_{3} \left[ {{\text{Ru}}\left( {\text{III}} \right)} \right] $$

and in view of the low Ru(III) concentrations used:

$$ \begin{aligned} \left[ {\textsc{d}} {\text{-Glu}} \right]_{\text{t}} & = \, \left[ {\textsc{d}} {\text{-Glu}} \right]_{\text{f}} \\ \left[ {{\text{Ru}}\left( {\text{III}} \right)} \right]_{t} & = \, \left[ {{\text{Ru}}\left( {\text{III}} \right)} \right]_{\text{f}} + [{\text{C}}] = \left[ {{\text{Ru}}\left( {\text{III}} \right)} \right]_{\text{f}} (1 + K_{3} \left[ {\textsc{d}} {\text{-Glu}} \right] \\ \end{aligned} $$
(A4)
$$ \left[ {{\text{Ru}}({\text{III}})} \right]_{\text{f}} = \frac{{\left[ {{\text{Ru}}({\text{III}})} \right]_{\text{t}} }}{{1 + K_{3} \left[ {\textsc{d}} {\text{-Glu}} \right]}} $$
(A5)

Substituting Eqs. A2–A5 into A1 gives:

$$ \begin{aligned} \frac{\text{rate}}{{\left[ {\text{DPA}} \right]}} & = k_{\text{C}} = k_{\text{T}} - k_{\text{U}} \\ & = \frac{{k_{1} K_{1} K_{2} K_{3} \left[ {\textsc{d}} {\text{-Glu}} \right]\left[ {{\text{OH}}^{ - } } \right]\left[ {{\text{Ru}}({\text{III}})} \right]}}{{\left[ {{\text{H}}_{3} {\text{IO}}_{6}^{2 - } } \right] + K_{1} \left[ {{\text{OH}}^{ - } } \right]\left[ {{\text{H}}_{3} {\text{IO}}_{6}^{2 - } } \right] + K_{1} K_{2} \left[ {{\text{OH}}^{ - } } \right] + K_{1} K_{2} K_{3} \left[ {{\text{OH}}^{ - } } \right]\left[ {\textsc{d}} {\text{-Glu}} \right]}} \\ \end{aligned} $$

The terms (K 3[\( {\text{H}}_{3} {\text{IO}}_{6}^{2 - } \)][d-Glu]) and (K 1 K 3[d-Glu][OH][\( {\text{H}}_{3} {\text{IO}}_{6}^{2 - } \)]) of the denominator are neglected in the view of low concentrations of d-Glu and periodate. Similarly, the rate law for the osmium(VIII) catalyzed reaction was similarly derived.

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Sataraddi, S.R., Nandibewoor, S.T. Oxidation of d-Glucose by Silver(III) Periodate Complex in the Presence of Ru(III)/Os(VIII) as a Homogeneous Catalyst: A Comparative Mechanistic Study (Stopped Flow Technique). J Solution Chem 42, 897–915 (2013). https://doi.org/10.1007/s10953-013-0002-1

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