Novel Reactivity of the Dioxygen Molecule in the Presence of a Manganese(II) Complex and Reducing Agents

Nishida, Yuzo; Tanaka, Noriko; Yamazaki, Akira; Tokii, Tadashi; Hashimoto, Noriyuki; Ide, Koji; Iwasawa, Kaku

doi:10.1021/ic00118a008

Cited by 30 publications

(18 citation statements)

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“…Some similar pre-peaks have previously been reported for Mn II complexes, [38,60] which were attributed to the reduction of dioxygen weakly bound to the metal center. [60] …”

Section: Anhydrous Dmso Solutionssupporting

confidence: 84%

“…It is known that, in anhydrous DMSO, the redox couple O 2 /O 2 Ϫ displays a reversible wave at E 1/2 ϭ Ϫ0.73 V vs. SCE. [18,24,55,60,61] We verified that under our experimental conditions, in the absence of any complex, this reversible wave was indeed observed. Its reversibility confirmed the anhydrous nature of the solvent under the experimental conditions.…”

Section: Anhydrous Dmso Solutionssupporting

confidence: 83%

“…In anhydrous DMSO, the redox couple O 2 /O 2 Ϫ shows a reversible wave at E 1/2 ϭ Ϫ0.73 V vs. SCE. [18,24,55,60,61] The same reversible wave was observed from a deoxygenated 0.1  Bu 4 NPF 6 /DMSO solution (15 min argon bubbling) to which a solution of KO 2 in the same electrolyte had been added ( Figure 5). This wave remained stable upon further deoxygenation, indicating that it was due to superoxide and not to dioxygen that might have resulted from superoxide disproportionation.…”

Section: Reactivity Of Mnipg and Mnbig Towards Superoxide In Anhydroumentioning

confidence: 52%

“…Such behavior is not uncommon for Mn II complexes. [38,60] When the cyclic voltammogram of MnIPG or MnBIG in DMSO was recorded without deoxygenation, an irreversible cathodic wave was observed, corresponding to the reduction of dioxygen to superoxide. It is known that, in anhydrous DMSO, the redox couple O 2 /O 2 Ϫ displays a reversible wave at E 1/2 ϭ Ϫ0.73 V vs. SCE.…”

Section: Anhydrous Dmso Solutionsmentioning

confidence: 99%

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New MnII Complexes with an N/O Coordination Sphere from TripodalN-Centered Ligands − Characterization from Solid State to Solution and Reaction with Superoxide in Non-Aqueous and Aqueous Media

Policar

Durot

Lambert

et al. 2001

Eur. J. Inorg. Chem.

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The crystal structure of a dimeric bis(µ-carboxylato)Mn II Mn II complex (2) with a tetradentate N-centered tripodal ligand, N,N-bis [(1-methylimidazol-2-yl)methyl]glycinate, is presented. The carboxylates are bridging monodentate. This complex shows some striking differences to the previously published parent compound 1 obtained with the closely related ligand N- [(1-methylimidazol-2-yl)methyl]-N-(2-pyridylmethyl)glycinate. The carboxylato bridges in both structures are shown to be disrupted in solution. The reactivities in solution of compounds 1 and 2 toward superoxide were

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“…Some similar pre-peaks have previously been reported for Mn II complexes, [38,60] which were attributed to the reduction of dioxygen weakly bound to the metal center. [60] …”

Section: Anhydrous Dmso Solutionssupporting

confidence: 84%

Section: Anhydrous Dmso Solutionssupporting

confidence: 83%

Section: Reactivity Of Mnipg and Mnbig Towards Superoxide In Anhydroumentioning

confidence: 52%

Section: Anhydrous Dmso Solutionsmentioning

confidence: 99%

See 2 more Smart Citations

New MnII Complexes with an N/O Coordination Sphere from TripodalN-Centered Ligands − Characterization from Solid State to Solution and Reaction with Superoxide in Non-Aqueous and Aqueous Media

Policar

Durot

Lambert

et al. 2001

Eur. J. Inorg. Chem.

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“…This should lead to formation of ternary complex among iron(III) compound, triplet oxygen and linolenic acid as illustrated in Scheme III, giving the product . It should be noted here that triplet oxygen interacting with unpaired electron of transition metal ions acts as a singlet oxygen ( 1  g ) towards several organic compounds Nishida, Tanaka, & Okazaki, 1994;Nishida et al, 1995;Nishida, 2004), and that the change of the oxidation state of Fe 3+ to the ferrous state (+2) is not necessary for the formation of hydroperoxy-derivarives, because both the high-and low-spin type iron(III) ion have unpaired d-electrons. In this study we have performed density functional computational study to validate our mechanism on oxygen activation in the Fe(III)-(cyclam) system and several lipoxygenase models.…”

Section: Scheme Imentioning

confidence: 96%

Oxygen Activation in Lipoxygenase Model Reaction Studied with Density Functional Theory

Nishida¹

2012

IJC

Self Cite

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Density Functional Computational studies were performed for the systems containing an iron (III) complex with (cyclam), 1,4-pentadiene and oxygen, where cyclam represents 1,4,8,11-tetraazacyclotetradecane. The calculations have indicated that bond formation between oxygen and carbon atom of the 1,4-pentadiene anion where methylene-proton is removed, occurs in the presence of the Fe III -(cyclam) complex, giving the hydroperoxy derivative of the 1,4-pentadiene. Based on these results it seems quite reasonable to assume that deprotonation of the methylene proton should be a trigger for the peroxidation of the 1,4-pentadiene moiety and the electron transfer reaction between iron(III) atom and the substrate is unnecessary in the lipoxygenases.

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Aerobic oxidation of styrene in functional reactors and computational fluid dynamics simulation

Zhang

Liu

et al. 2018

Asia-Pacific J Chem Eng

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A possible reaction mechanism was proposed, and the kinetic relationships between rate of styrene conversion (or product generation) and condition parameters were established for the aerobic oxidation of styrene by using isobutyraldehyde as coreductant and cobalt(II) acetate as catalyst. The effects of aldehyde amount, catalyst amount, and volume ratio of solvent to styrene on the total yield of products (styrene oxide and benzaldehyde) were evaluated by the response surface methodology systematically. Relative mathematical models were presented to reveal the optimal reaction conditions, which were used for further scale-up experiments in bubbling column reactor and airlift loop reactor. The 2 reactors had different results due to structural characteristics. Larger gas holdup and longer gas residence time led to higher styrene conversion in the bubbling column reactor, whereas faster and regular liquid circulation resulted in higher styrene oxide selectivity in the airlift loop reactor due to better dispersion of solid catalyst. Furthermore, the different performances of the 2 reactors were explained with computational fluid dynamics by considering turbulence intensity, axial velocity distribution, gas holdup, and volumetric mass transfer coefficient.

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Novel Reactivity of the Dioxygen Molecule in the Presence of a Manganese(II) Complex and Reducing Agents

Cited by 30 publications

References 0 publications

New MnII Complexes with an N/O Coordination Sphere from TripodalN-Centered Ligands − Characterization from Solid State to Solution and Reaction with Superoxide in Non-Aqueous and Aqueous Media

New MnII Complexes with an N/O Coordination Sphere from TripodalN-Centered Ligands − Characterization from Solid State to Solution and Reaction with Superoxide in Non-Aqueous and Aqueous Media

Oxygen Activation in Lipoxygenase Model Reaction Studied with Density Functional Theory

Aerobic oxidation of styrene in functional reactors and computational fluid dynamics simulation

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