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Maji, Dilip; Das, Prabal; Banerjee, Rupendranath

doi:10.1023/a:1013404902339

Cited by 7 publications

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“…N ] 4ϩ to a mixed Mn III Mn IV species catalysed by Mn 2ϩ is proposed to be an inner-sphere process involving N 2 H 5 ϩ , as is the oxidation of the equivalent phenanthroline complex by H 2 O. 58, 59 Reduction of trans-[Mn III (cyclam)Cl 2 ] ϩ by hydroquinone occurs via an inner-sphere mechanism, 60 whereas the reaction of [Mn 2 III/IV (µ-O) 2 (cyclam) 2 ] 3ϩ with benzene diols appear to be outer-sphere. Linking the mechanisms of oxidation of hydrocarbons by bis-µ-oxomanganese dimers with energetics and intrinsic barriers suggests these govern whether the processes occur by electron-, hydrogen atom-or hydride-transfer.…”

Section: Inner-sphere Electron and Atom Transfermentioning

confidence: 99%

26 Mechanisms of reactions in solution

Davies

2003

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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This year has seen the first Dalton Discussion in Inorganic Reaction Mechanisms. 1 This was an extremely interesting development. The overall theme was Inorganic Reaction Mechanisms: insights into chemical challenges and there were Dalton Perspectives papers in each of the themes: Applications of advanced experimental techniques, Advanced computational techniques, Small molecule activation, homogenous catalysis, Electron and energy transfer processes and Bioinorganic applications. These are to be found in the special March issue of Dalton and form a very good in-depth overview of the subject. The sessions on advanced instrumental and computational techniques covered the areas which will undoubtedly have a major effect on inorganic reaction mechanisms in the future: one by eventually allowing routine rate measurements of faster and faster reactions and the other by providing the theoretical background to the subject.As in previous years this review does not cover mechanisms of heterogeneous or solid state process, homogeneous catalysis of organic reactions, fluxional, electrochemical and photochemical processes, redox reactions involving organic substrates or organic reactions of the p-block elements.The fundamentals of theoretical modelling techniques used to calculate molecular energies and rate parameters for inorganic reactions have been described 2 and the phenomenon of so-called "phantom activation volumes" has been investigated and shown to be real activation volumes. 3 Redox reactions Long range electron transferReviews have appeared on aspects of charge-transfer processes in DNA, 4 the application of high pressure techniques to electron transfer reactions particularly in proteins and related species 5 and a theoretical analysis of donor-acceptor electron transfer, particularly super-exchange and thermally activated, mechanisms involving linear molecular bridges has appeared. 6 Electron transfer rates between the non-covalently bound flavine group at the active site to the surface of the protein in flavocytochrome c 3 from Shewanella frigidimarima

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Section: Inner-sphere Electron and Atom Transfermentioning

confidence: 99%

26 Mechanisms of reactions in solution

Davies

2003

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Kinetics and Mechanism of Oxidation of Fe²⁺ by the Tris(biguanide)manganese(IV) Ion in Aqueous Acid Media

et al. 2004

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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 (> 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 Fe3+, 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(LH2)3]3+, the initial one‐electron‐reduced product of MnIV, is believed to be a steady‐state intermediate. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Mechanistic Investigation of the Oxidation of Glyoxylic and Pyruvic Acids by Tris(biguanide)manganese(IV) in Weakly Acidic Aqueous Media

et al. 2004

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In this study the kinetics of two electron transactions between the reducing substrates glyoxylic and pyruvic acids and the oxidising complex cation, tris(biguanide)manganese(IV) in aqueous acidic media have been examined. Under the experimental conditions (pH = 1.50−3.78) only the fully protonated form of the oxidant reacts with the anions of the substrates whereas the parent acids, viz. glyoxylic and pyruvic acids, were found to be unreactive. The second-order

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Untitled

Cited by 7 publications

References 16 publications

26 Mechanisms of reactions in solution

26 Mechanisms of reactions in solution

Kinetics and Mechanism of Oxidation of Fe²⁺ by the Tris(biguanide)manganese(IV) Ion in Aqueous Acid Media

Mechanistic Investigation of the Oxidation of Glyoxylic and Pyruvic Acids by Tris(biguanide)manganese(IV) in Weakly Acidic Aqueous Media

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Untitled

Cited by 7 publications

References 16 publications

26 Mechanisms of reactions in solution

26 Mechanisms of reactions in solution

Kinetics and Mechanism of Oxidation of Fe2+ by the Tris(biguanide)manganese(IV) Ion in Aqueous Acid Media

Mechanistic Investigation of the Oxidation of Glyoxylic and Pyruvic Acids by Tris(biguanide)manganese(IV) in Weakly Acidic Aqueous Media

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Kinetics and Mechanism of Oxidation of Fe²⁺ by the Tris(biguanide)manganese(IV) Ion in Aqueous Acid Media