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Shiv Nadar University

Tris(biguanide)manganese(IV), [Mn(LH2)3]4+ (LH2 = biguanide, C2N5H7), quantitatively oxidises Fe2+ to Fe3+ and is itself reduced to Mn2+ with almost quantitative (&gt; 95%) release of biguanide, The reaction rate strongly depends on added Fe3+; in the presence of externally added Fe3+, the reaction shows a clear first-order dependence in [MnIV], whereas in the absence of any added Fe 3+, an initial quick loss of MnIV is associated with a subsequent very sluggish decay. Two consecutive one-electron transfer inner-sphere steps are proposed for the entire redox process where [Mn(LH 2)3]3+, the initial one-electron-reduced product of MnIV, is believed to be a steady-state intermediate. © Wiley-VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2004.

Chemistry

(SoNS) School of Natural Sciences

World University root node

European Journal of Inorganic Chemistry

Kinetics and mechanism of oxidation of Fe2+ by the tris(biguanide)manganese(IV) ion in aqueous acid media

In aqueous acidic media sodium azide and the orange-yellow title complex react quantitatively generating N2 gas along with a colourless solution of Ag+ ion and the ligand, ethylenebis(biguanide). The parent complex, [Ag(H2L)]3+, and one of its conjugate bases, [Ag(HL)]2+, participate in the reaction with N 3- as the kinetically reactive reductant. Ag+ has no catalytic effect. At 25.0 °C, I = 1.0 M (NaNO3), rate constants for the reactions [Ag(H2L)]3+ + N 3- and that for [Ag(HL)]2+ + N3 - are (12.3±0.5) and (3.8±0.6) M-1· S-1, respectively. The high rate constants along with the very low equilibrium constant (10-15 M-1) calculated for the first reaction strongly suggest inner-sphere redox mechanism. © Wiley-VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2003.