Kinetics and mechanism of hydrazine oxidation by a tri-bridged manganese(IV,IV) dimer in weakly acidic media

Mondal, Anath Bandhu; Bhattacharya, Anup; Maji, Dilip; Banerjee, Rupendranath

doi:10.1016/s0277-5387(97)00441-5

Polyhedron

1998

DOI: 10.1016/s0277-5387(97)00441-5

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Kinetics and mechanism of hydrazine oxidation by a tri-bridged manganese(IV,IV) dimer in weakly acidic media

Anath Bandhu Mondal

Anup Bhattacharya

Dilip Maji

et al.

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Cited by 13 publications

References 42 publications

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Kinetic and Mechanistic Studies on the Oxidation of Nitrogen(III) (HNO₂/$\rm{{{NO}}_2^ - }$) by the Tris(biguanide)manganese(IV) Ion in Aqueous Acidic Media

Das¹,

Mukhopadhyay²

2005

Helvetica Chimica Acta

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The kinetics of a net two‐electron transfer between an authentic MnIV complex, [Mn(bigH)3]4+ (Fig. 1; bigH = biguanide = C2N5H7), and nitrite in aqueous solution in the pH interval 2.00–3.60 is described. Stoichiometric data for the reaction clearly indicates Δ[MnIV]/Δ[NIII]T = 1.07 ± 0.10, and $\rm{{{NO}}_3^ - }$ is detected as the oxidized product of nitrite ([NIII]T = [HNO2] + [$\rm{{{NO}}_2^ - }$]). Though both HNO2 and $\rm{{{NO}}_2^ - }$ are found to be reactive, the latter is kinetically superior in reducing the fully protonated MnIV complex. Proton‐coupled electron transfer (PCET; 1e, 1H+) reduces the activation barrier for the thermodynamically unfavorable reaction of weakly oxidizing MnIV species. At the end of the redox process, the ligand bigH is released, and the high protonation constants of the ligand carry the overall reaction to completion.

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Kinetic and Mechanistic Studies on the Oxidation of Nitrogen(III) (HNO₂/$\rm{{{NO}}_2^ - }$) by the Tris(biguanide)manganese(IV) Ion in Aqueous Acidic Media

Das¹,

Mukhopadhyay²

2005

Helvetica Chimica Acta

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Mechanistic studies on the oxidation of glyoxylic and pyruvic acids by a {Mn₃O₄}⁴⁺ core in aqueous media

Mandal

Das

Mukhopadhyay

2010

Int J of Chemical Kinetics

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In aqueous media, the Mn IV trimer [Mn IV 3 (μ-O) 4 (phen) 4 (H 2 O) 2 ] 4+ (1, phen = 1,10phenanthroline) equilibrates with its deprotonated from [Mn 3 (μ-O) 4 (phen) 4 (H 2 O)(OH)] 3+ (2). Among the several synthetic multinuclear oxo-and/or carboxylato-bridged manganese complexes known to date containing metal-bound water, to the best of our knowledge, 1 is one of the rare examples that deprotonates (1 2 + H + ; pK a = 4.00 (±0.15) at 25.0 • C, I = 1.0 mol dm −3 , maintained with NaNO 3 ) at physiological pH. In aqueous media (pH 2-4), 1 oxidizes both glyoxylic and pyruvic acids to formic and acetic acid, respectively, along with the formation of CO 2 , the end manganese state being Mn II . Kinetic studies suggest that the species 1, its deprotonated form 2, the reducing acids (HA), and their conjugate bases (A − ) all take part in the reaction. The oxidant 1 is found to be more reactive than its conjugate base 2, and HA reacts faster than A − in reducing 1 or 2. The gem-diol form of the α-oxo acids (especially for glyoxylic acid) is the possible reducing species. The Mn IV 3 to Mn II transition in the present observation proceeds through the intermediate generation of the spectrally characterized mixed-valent Mn III Mn IV dimer that quickly collapses to Mn II . The observed rates of glyoxylic or pyruvic acid oxidation do not depend on the variation of 1,10-phenanthroline content of the solution, indicating the absence of any phen-releasing preequilibrium of the title complex in solution. The reactions rates were found to be lowered in media enriched with D 2 O in comparison to that in H 2 O and a rate-limiting one electron one proton (1e, 1H + ) electroprotic mechanism is proposed. C

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Kinetic studies on oxidation of l-cysteine and 2-mercaptoethanol by a trinuclear Mn(IV) species in aqueous acidic media

Chakraborty

Mandal

Mukhopadhyay

2013

Inorganica Chimica Acta

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Kinetics and mechanism of hydrazine oxidation by a tri-bridged manganese(IV,IV) dimer in weakly acidic media

Cited by 13 publications

References 42 publications

Kinetic and Mechanistic Studies on the Oxidation of Nitrogen(III) (HNO₂/$\rm{{{NO}}_2^ - }$) by the Tris(biguanide)manganese(IV) Ion in Aqueous Acidic Media

Kinetic and Mechanistic Studies on the Oxidation of Nitrogen(III) (HNO₂/$\rm{{{NO}}_2^ - }$) by the Tris(biguanide)manganese(IV) Ion in Aqueous Acidic Media

Mechanistic studies on the oxidation of glyoxylic and pyruvic acids by a {Mn₃O₄}⁴⁺ core in aqueous media

Kinetic studies on oxidation of l-cysteine and 2-mercaptoethanol by a trinuclear Mn(IV) species in aqueous acidic media

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Kinetics and mechanism of hydrazine oxidation by a tri-bridged manganese(IV,IV) dimer in weakly acidic media

Cited by 13 publications

References 42 publications

Kinetic and Mechanistic Studies on the Oxidation of Nitrogen(III) (HNO2/$\rm{{{NO}}_2^ - }$) by the Tris(biguanide)manganese(IV) Ion in Aqueous Acidic Media

Kinetic and Mechanistic Studies on the Oxidation of Nitrogen(III) (HNO2/$\rm{{{NO}}_2^ - }$) by the Tris(biguanide)manganese(IV) Ion in Aqueous Acidic Media

Mechanistic studies on the oxidation of glyoxylic and pyruvic acids by a {Mn3O4}4+ core in aqueous media

Kinetic studies on oxidation of l-cysteine and 2-mercaptoethanol by a trinuclear Mn(IV) species in aqueous acidic media

Contact Info

Product

Resources

About

Kinetic and Mechanistic Studies on the Oxidation of Nitrogen(III) (HNO₂/$\rm{{{NO}}_2^ - }$) by the Tris(biguanide)manganese(IV) Ion in Aqueous Acidic Media

Kinetic and Mechanistic Studies on the Oxidation of Nitrogen(III) (HNO₂/$\rm{{{NO}}_2^ - }$) by the Tris(biguanide)manganese(IV) Ion in Aqueous Acidic Media

Mechanistic studies on the oxidation of glyoxylic and pyruvic acids by a {Mn₃O₄}⁴⁺ core in aqueous media