Ligand substitution and electron transfer reactions of trans-(diaqua)(salen)manganese(<scp>iii</scp>) with oxalate: an experimental and computational study

Kar, Akshaya K.; Acharya, Achyut N.; Mundlapati, V. Rao; Pradhan, Guru C.; Biswal, Himansu S.; Dash, Anadi C.

doi:10.1039/c4ra10324f

Cited by 4 publications

(12 citation statements)

References 35 publications

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“…Figure 1(a) and 1(b) depict the six-line ESR spectrum of the reaction mixture characteristic of Mn II 1,2,13 establishing that the reaction we followed under different conditions of pH is in fact reduction of Mn III in salophen scaffold by oxalate species. This is in line with what we reported earlier for the corresponding Mn III (Salen) complex.…”

Section: Product Analysis and Stoichiometrymentioning

confidence: 81%

“…This is in line with what we reported earlier for the corresponding Mn III (Salen) complex. 2 Based on these observations we assign the stoichiometry of the overall reaction as follows: (Salen). 2 The formation of the oxalate radical(C 2 O −.…”

Section: Product Analysis and Stoichiometrymentioning

confidence: 99%

“…2 Based on these observations we assign the stoichiometry of the overall reaction as follows: (Salen). 2 The formation of the oxalate radical(C 2 O −. 4 ) and its decomposition product, CO −.…”

Section: Product Analysis and Stoichiometrymentioning

confidence: 99%

“…The pH dependence of k obs ,however, indicates that OX 2− contrastingly is a much weaker reducing species than HOX − ( Figure 5) in the present context further supporting our earlier observation on the Mn III (Salen) + oxalate. 2 Scheme 2, in addition to Scheme 1, is proposed to interpret the rate data (see Table 1 and Table S1a,b in Supplementary Information). Accordingly, k obs takes the form:…”

Section: Analysis Of the Kinetic Datamentioning

confidence: 99%

“…Previously we have reported the redox reactions of Mn III (Salen) + by glyoxylate 1 and oxalate. 2 The redox process involves fast pre-equilibrium of the glyoxalate and oxalate species followed by slow electron transfer reactions between Mn III (Salen)X (X = glyoxylate, HOX − , OX 2− ) and the corresponding acids, and their anions. It turned out that the binding of ligand X to Mn III centre considerably stabilized Mn III centre for intramolecular electron transfer in Mn III (Salen)X.…”

Section: Introductionmentioning

confidence: 99%

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Kinetics and mechanistic study of the reduction of $$\hbox {Mn}^{\mathrm{III}}$$ Mn III by oxalate in Salophen scaffold: relevance to oxalate oxidase

et al. 2018

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The trans-Mn III (Salophen)(OH 2) 2 + and bioxalate (HOX −) in aqueous medium equilibrate rapidly to trans-Mn III (Salophen)(OH 2)(HOX) followed by the acid dissociation equilibrium to the (aqua) mono oxalato complex. The slow redox reactions of trans-Mn III (Salophen)(OH 2)(HOX/OX) 0/− with H 2 OX, HOX − ,OX 2− obey second order kinetics satisfying 2:1 stoichiometry ([Mn III ] T /[OX] T = 2/1). The products are Mn II and CO 2. Acrylamide monomer has no effect on the rate constant and the reaction does not induce its polymerization. The rate and activation parameters for the various rate limiting paths are reported. The intramolecular reduction of Mn III by the coordinated HOX − and OX 2− in trans-Mn III (Salophen)(OH 2)(HOX/OX) 0/− could not be detected. Contrary to our expectation, it is observed that H 2 OX is a better reducing agent than HOX − for trans-Mn III (Salophen)(OH 2)(HOX), the slowest being the redox reaction of OX 2− with trans-Mn III (Salophen)(OH 2)(OX) −. The molecular modelling by DFT depicts the structural trans effect in the oxalato complexes, it being maximum for trans-Mn III (Salophen)(OH 2)(OX) −. The observed sequence of the redox activity of the oxalato complexes reflects the potential role of non-covalent interaction i.e. H-bonding, governing the proton controlled electron transfer process (PCET). The Mn III (Salophen/Salen) complexes may turn out to be good substitute candidates for Oxalo Oxidase (OXO) enzyme in alleviating the oxalate overload in plants and animal biochemistry.

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Section: Product Analysis and Stoichiometrymentioning

confidence: 81%

Section: Product Analysis and Stoichiometrymentioning

confidence: 99%

Section: Product Analysis and Stoichiometrymentioning

confidence: 99%

Section: Analysis Of the Kinetic Datamentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Kinetics and mechanistic study of the reduction of $$\hbox {Mn}^{\mathrm{III}}$$ Mn III by oxalate in Salophen scaffold: relevance to oxalate oxidase

et al. 2018

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A novel oxalated zero-valent iron nanoparticle for Pb(II) removal from aqueous solution: Performance and synergistic mechanisms

Dai

et al. 2022

Separation and Purification Technology

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Oxalate Modification Dramatically Promoted Cr(VI) Removal with Zero-Valent Iron

et al. 2021

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In this study, we demonstrated that oxalate modification could promote the Cr(VI) removal performance of zerovalent iron (ZVI) and increase the removal rate constant by about 20 times. This dramatic enhancement of Cr(VI) removal was attributed to the binding of oxalate groups on the surface of ZVI in a monodentate mononuclear configuration. The surface structure of oxalate-modified zerovalent iron (OA-ZVI) and the Cr(VI) adsorption behaviors on ZVI and OA-ZVI were carefully investigated. The theoretical results revealed that this oxalate modification favored Cr(VI) adsorption on the ZVI surface with a much lower adsorption energy and also accelerated electrons transfer from the iron core to the surface, which could produce more surface Fe(II) to easily reduce Cr(VI) via a single electron transfer pathway, greatly promoting the reduction removal of Cr(VI). More importantly, OA-ZVI still remained at a high Cr(VI) removal activity even after six cycles of use for both simulated and real Cr(VI)-containing wastewaters, revealing its excellent continuous Cr(VI) removal ability for practical application. This study provides an environmental-benignity surface modification method of ZVI and also highlights the importance of surface functional groups on the Cr(VI) removal property of ZVI.

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Ligand substitution and electron transfer reactions of trans-(diaqua)(salen)manganese(iii) with oxalate: an experimental and computational study

Abstract: MnIII(salen)(OH2)2+ undergoes reversible anation by HOX−via Ia mechanism followed by proton controlled electron transfer involving MnIII(salen)(HOX) and H2OX.

Cited by 4 publications

References 35 publications

Kinetics and mechanistic study of the reduction of $$\hbox {Mn}^{\mathrm{III}}$$ Mn III by oxalate in Salophen scaffold: relevance to oxalate oxidase

Kinetics and mechanistic study of the reduction of $$\hbox {Mn}^{\mathrm{III}}$$ Mn III by oxalate in Salophen scaffold: relevance to oxalate oxidase

A novel oxalated zero-valent iron nanoparticle for Pb(II) removal from aqueous solution: Performance and synergistic mechanisms

Oxalate Modification Dramatically Promoted Cr(VI) Removal with Zero-Valent Iron

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