Kinetics and mechanism of oxidation of fumarate, acrylate, cinnamate, and maleate anions by hexavalent manganese in aqueous alkaline medium

Sreenivasulu, P. V.; Adinarayana, M.; Sethuram, B.; Rao, T. Navaneeth

doi:10.1002/kin.550170908

Cited by 7 publications

(4 citation statements)

References 6 publications

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“…70,75 It also has been demonstrated that Mn(V) could oxidize sulfoxide and olefin moieties via oxygen-atom transfer or alkene addition reaction. 76,77 The results in this study also showed rapid degradation of BPA containing phenolic moiety and SMX and MB with sulfoxide moiety.…”

supporting

confidence: 60%

“…There are few available rate constants for the reaction of high-valent Mn species with MPs, but it has been demonstrated that Mn(V) has high reactivities with a range of MPs containing electron-rich moieties such as phenolic, olefin, and sulfoxide . High reactivity of Mn(V) toward phenolic compounds could be due to the ability to generate O-bridged compounds, allowing inner-sphere electron transfer. , It also has been demonstrated that Mn(V) could oxidize sulfoxide and olefin moieties via oxygen-atom transfer or alkene addition reaction. , The results in this study also showed rapid degradation of BPA containing phenolic moiety and SMX and MB with sulfoxide moiety.…”

Section: Resultsmentioning

confidence: 99%

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Picolinic Acid-Mediated Catalysis of Mn(II) for Peracetic Acid Oxidation Processes: Formation of High-Valent Mn Species

Kim

Wang

Ashley

et al. 2023

Environ. Sci. Technol.

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Metal-based advanced oxidation processes (AOPs) with peracetic acid (PAA) have been extensively studied to degrade micropollutants (MPs) in wastewater. Mn(II) is a commonly used homogeneous metal catalyst for oxidant activation, but it performs poorly with PAA. This study identifies that the biodegradable chelating ligand picolinic acid (PICA) can significantly mediate Mn(II) activation of PAA for accelerated MP degradation. Results show that, while Mn(II) alone has minimal reactivity toward PAA, the presence of PICA accelerates PAA loss by Mn(II). The PAA-Mn(II)-PICA system removes various MPs (methylene blue, bisphenol A, naproxen, sulfamethoxazole, carbamazepine, and trimethoprim) rapidly at neutral pH, achieving >60% removal within 10 min in clean and wastewater matrices. Coexistent H 2 O 2 and acetic acid in PAA play a negligible role in rapid MP degradation. In-depth evaluation with scavengers and probe compounds (tert-butyl alcohol, methanol, methyl phenyl sulfoxide, and methyl phenyl sulfone) suggested that high-valent Mn species (Mn(V)) is a likely main reactive species leading to rapid MP degradation, whereas soluble Mn(III)-PICA and radicals (CH 3 C(O)O • and CH 3 C(O)OO • ) are minor reactive species. This study broadens the mechanistic understanding of metal-based AOPs using PAA in combination with chelating agents and indicates the PAA-Mn(II)-PICA system as a novel AOP for wastewater treatment.

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supporting

confidence: 60%

Section: Resultsmentioning

confidence: 99%

Picolinic Acid-Mediated Catalysis of Mn(II) for Peracetic Acid Oxidation Processes: Formation of High-Valent Mn Species

Kim

Wang

Ashley

et al. 2023

Environ. Sci. Technol.

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“…Selected bond lengths are collected in Table 3. In the bidentate ligand of complex [4], the bond lengths of N1−C1 and N2−C6 are 1.340 (8) and 1.362(8) Å, respectively, and appreciably longer than the corresponding bond lengths in [2] + . Moreover, the bond lengths of C1−C2, C2−C3, C3−C4, C4−C5, C5−C6, and C6−C1 of the phenyl ring are 1.397 (9), 1.361 (9), 1.396(11), 1.369 (9), 1.399( 9), and 1.413(10) Å, respectively, and are all long.…”

Section: Inorganic Chemistrymentioning

confidence: 99%

“…Notably, this class of reactions proceeds via aromatic ring C–H activation, which are otherwise difficult in aromatic amines because of the electron richness of the aromatic ring . Oxidation of aromatic amines thus in most cases result in azo, azoxy, or hydrazo compounds, though formation of polyanilines has been reported only under strong reaction conditions . In comparison, regioselective ortho -C–N bond fusion reactions of aromatic amines are still limited in the literature.…”

Section: Introductionmentioning

confidence: 99%

Role of Mediator and Effects of Temperature on ortho-C–N Bond Fusion Reactions of Aniline Using Ruthenium Templates: Isolation and Characterization of New Ruthenium Complexes of the in-Situ-Generated Ligands

et al. 2017

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In this work, ortho-C-N bond fusion reactions of aniline are followed by the use of two different ruthenium mediators. Reaction of aniline with [Ru(terpy)Cl] (terpy = 2,2':6',2″-terpyridine) resulted in a trans bis-aniline ruthenium(II) complex [1] which upon oxidation with HO produced compound [2] of a bidentate ligand, N-phenyl-1,2-benzoquinonediimine, due to an oxidative ortho-C-N bond fusion reaction. Complex [1] and aniline (neat) at 185 °C produced a bis-chelated ruthenium complex (3). A previously reported complex [Ru(N-phenyl-1,2-benzoquinonediimine)(aniline)(Cl)] (5) undergoes similar oxidation by air at 185 °C to produce complex [3]. A separate chemical reaction between aniline and strongly oxidizing tetra-n-propylammonium perruthenate [(n-pr)N][RuO] in air produced a ruthenium complex [4] of a N-tetraamidophenylmacrocycle ligand via multiple ortho-C-N bond fusion reaction. Notably, the yield of this product is low (5%) at 100 °C but increases to 25% in refluxing aniline. All these complexes are characterized fully by their physicochemical characterizations and X-ray structure determination. From their structural parameters and other spectroscopic studies, complex [2] is assigned as [Ru(terpy)(N-phenyl-1,2-benzoquinonediimine)(Cl)] whereas complex [4] is described as a ruthenium(VI) complex comprised of a reduced deprotonated N-phenyl-1,2-diamidobenzene and N-tetraamidophenylmacrocyclic ligand. Complex [2] exhibits one reversible oxidation at 1.32 V and one reversible reduction at -0.75 V vs Ag/AgCl reference electrode. EPR of the electrogenerated complexes has revealed that the oxidized complex is a ruthenium(III) complex with an axial EPR spectrum at g= 2.06. The reduced complex [2], on the other hand, shows a single-line EPR signal at g= 1.998. In contrast, complex [4] shows two successive one-electron oxidation waves at 0.5 and 0.8 V and an irreversible reduction wave at -0.9 V. EPR studies of the oxidized complexes [4] and [4] reveal that oxidations are ligand centered. DFT calculations were employed to elucidate the electronic structures as well as the redox processes associated with the above complexes. Aerial ortho-C-N bond fusion reactions of aniline using two different mediators, viz. [Ru(terpy)Cl] and [(n-pr)N][RuO], have been followed. It is found that in the case of oxidizable Ru(III) mediator complex, C-N bond fusion is limited only to dimerization reaction whereas the high-valent Ru(VII) salt mediates multiple C-N bond fusion reactions leading to the formation of a novel tetradentate N-tetraamidophenylmacrocyclic ligand. Valence ambiguity in the complexes of the resultant redox-active ligands is scrutinized.

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ChemInform Abstract: Kinetics and Mechanism of Oxidation of Fumarate, Acrylate, Cinnamate, and Maleate Anions by Hexavalent Manganese in Aqueous Alkaline Medium (Reaktion folgt Michaelis‐Menten‐Kinetik).

Sreenivasulu¹,

Adinarayana²,

Sethuram³

et al. 1986

Chemischer Informationsdienst

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Kinetics and mechanism of oxidation of fumarate, acrylate, cinnamate, and maleate anions by hexavalent manganese in aqueous alkaline medium

Cited by 7 publications

References 6 publications

Picolinic Acid-Mediated Catalysis of Mn(II) for Peracetic Acid Oxidation Processes: Formation of High-Valent Mn Species

Picolinic Acid-Mediated Catalysis of Mn(II) for Peracetic Acid Oxidation Processes: Formation of High-Valent Mn Species

Role of Mediator and Effects of Temperature on ortho-C–N Bond Fusion Reactions of Aniline Using Ruthenium Templates: Isolation and Characterization of New Ruthenium Complexes of the in-Situ-Generated Ligands

ChemInform Abstract: Kinetics and Mechanism of Oxidation of Fumarate, Acrylate, Cinnamate, and Maleate Anions by Hexavalent Manganese in Aqueous Alkaline Medium (Reaktion folgt Michaelis‐Menten‐Kinetik).

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