Mechanisms of Reduction of trans-Cyclohexane-1,2-diamine-NNN'N'-tetra-acetatomanganate(III) by Hydrazine, Hydroxylamine, and Substituted Benzene-1,2-diols

DOI: 10.1039/DT9830000689

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 689 - 696 (1983)

Update date:2022-08-10

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Authors:

Arselli, Patrizia

Mentasti, Edoardo

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Article abstract of DOI:10.1039/DT9830000689

The kinetics and mechanism of reduction of trans-cyclohexane-1,2-diamine-NNN'N'-tetra-acetatomanganate(III), III(cdta)(H₂O)>^-, by hydrazine hydroxylamine, and a series of substituted benzene-1,2-diols C₆H₃(OH)₂R (R=H, 4-Me, 4-CO₂H, or 3-CO₂H) have been investigated by the stopped-flow technique.Simple first-order dependence on Mn^III complex and reductant concentrations has been observed for hydrazine, which shows a rate with +>^-1 dependence.For hydroxylamine, complex kinetic dependences on reductant and hydrogen-ion concentration suggest a composite inner-sphere mechanism.Also, in the case of the diols an inner-sphere mechanism, through intermediate association, is proposed; for these substrates experimental rates, higher than those computed with the Marcus cross relation, and limiting kinetics are in agreement with the lability of the oxidizing complex.

Full text of DOI:10.1039/DT9830000689

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