Manganese(II) Semiquinonato and Manganese(III) Catecholato Complexes with Tridentate Ligand: Modeling the Substrate‐Binding State of Manganese‐Dependent Catechol Dioxygenase and Reactivity with Molecular Oxygen

Komatsuzaki, Hidehito; Shiota, Akihiko; Hazawa, Shogo; Itoh, Muneaki; Miyamura, Noriko; Miki, Nahomi; Takano, Yoichi; Nakazawa, Jun; Inagaki, Akiko; Akita, Munetaka; Hikichi, Shiro

doi:10.1002/asia.201300029

Cited by 9 publications

(4 citation statements)

References 90 publications

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“…Upon reaction with O 2 in THF for 16 hours, [PhTt tBu ]Co(3,5-DBSQ) produced the intradiol cleavage product, muconic anhydride in 16% yield, Scheme 1 (see ESI † for details). This result, together with a previous discovery that the five coordinate complex [Tp iPr2 ]Mn(3,5-DBSQ) also produces the intradiol product, 22 suggests that the semiquinonate character of the ligand may contribute to the intradiol cleaving reactivity, even for different metals. To the best of our knowledge, this is the first example of intradiol reactivity of a Co II (3,5-DBSQ) complex.…”

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confidence: 53%

Five-coordinate M^II-semiquinonate (M = Fe, Mn, Co) complexes: reactivity models of the catechol dioxygenases

2014

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A series of five-coordinate M(II)-semiquinonate (M = Fe, Mn, Co) complexes were synthesized and characterized, including the first example of a mononuclear Fe(II)-semiquinonate. Intermediates were observed in the reactions of M(II)-phenSQ (M = Fe, Co) with O2. Evidence for the relevance of these intermediates to the intradiol catechol dioxygenases was obtained by characterization of the oxidized semiquinone-derived product, muconic anhydride, resulting from the reaction of [PhTt(tBu)]Co(II)(3,5-DBSQ) with O2.

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confidence: 53%

Five-coordinate M^II-semiquinonate (M = Fe, Mn, Co) complexes: reactivity models of the catechol dioxygenases

2014

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“…This oxidation has attracted much attention as a green chemistry approach for the conversion of aromatic compounds to water-soluble products and for degradation of lignin [ 575 – 576 ]. The ring cleavage of 1,2-dihydroxybenzene (catechol) is likely the most thoroughly studied reaction which is catalyzed by iron-dependent catechol dioxygenase enzymes [ 577 – 579 ]. The oxidation of catechols 671 and 673 by two types of enzymes – intradiol dioxygenase and extradiol dioxygenase – affords 3-carboxyhexa-2,4-dienedioic acid ( 672 ) and 2-hydroxy-6-ketonona-2,4-dienoic acid ( 674 ) ( Scheme 187 ) [ 580 – 581 ].…”

Section: Reviewmentioning

confidence: 99%

Rearrangements of organic peroxides and related processes

Yaremenko¹,

Vil²,

Demchuk³

et al. 2016

Beilstein J. Org. Chem.

182

136

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SummaryThis review is the first to collate and summarize main data on named and unnamed rearrangement reactions of peroxides. It should be noted, that in the chemistry of peroxides two types of processes are considered under the term rearrangements. These are conventional rearrangements occurring with the retention of the molecular weight and transformations of one of the peroxide moieties after O–O-bond cleavage. Detailed information about the Baeyer−Villiger, Criegee, Hock, Kornblum−DeLaMare, Dakin, Elbs, Schenck, Smith, Wieland, and Story reactions is given. Unnamed rearrangements of organic peroxides and related processes are also analyzed. The rearrangements and related processes of important natural and synthetic peroxides are discussed separately.

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“…For the remaining compounds, O 2 reduction is not arrested in the two-electron stage because of the poor stability of the intermediate semiquinonato compound. That probably explains why only a few semiquinonato compounds of manganese(III) have been reported thus far in the literature. , Dioxolene oxidation during the formation of compounds 3 – 6 proceeds further up to the quinonato stage with concomitant four-electron reduction of O 2 .…”

Section: Resultsmentioning

confidence: 99%

Ligand-Induced Tuning of the Oxidase Activity of μ-Hydroxidodimanganese(III) Complexes Using 3,5-Di-tert-butylcatechol as the Substrate: Isolation and Characterization of Products Involving an Oxidized Dioxolene Moiety

et al. 2017

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Oxidase activities of a μ-hydroxidodimanganese(III) system involving a series of tetradentate capping ligands HL with a pair of phenolate arms have been investigated in the presence of 3,5-di-tert-butylcatechol (HDBC) as a coligand cum-reductant. The reaction follows two distinctly different paths, decided by the substituent combinations (R and R) present in the capping ligand. With the ligands HL and HL, the products obtained are semiquinonato compounds [Mn(L)(DBSQ)]·2CHOH (1) and [Mn(L)(DBSQ)]·CHOH (2), respectively. In the process, molecular oxygen is reduced by two electrons to generate HO in the solution, as confirmed by iodometric detection. With the rest of the ligands, viz., HL, HL, HL, and HL, the products initially obtained are believed to be highly reactive quinonato compounds [Mn(L)(DBQ)], which undergo a domino reaction with the solvent methanol to generate products of composition [Mn(L)(BMOD)] (3-6) involving a nonplanar dioxolene moiety, viz., 3,5-di-tert-butyl-3-methoxy-6-oxocyclohexa-1,4-dienolate (BMOD). This novel dioxolene derivative is formed by a Michael-type nucleophilic 1,4-addition reaction of the methoxy group to the coordinated quinone in [Mn(L)(DBQ)]. During this reaction, molecular oxygen is reduced by four electrons to generate water. The products have been characterized by single-crystal X-ray diffraction analysis as well as by spectroscopic methods and magnetic measurements. Density functional theory calculations have been made to address the observed influence of the secondary coordination sphere in tuning the two-electron versus four-electron reduction of dioxygen. The semiquinone form of the dioxolene moiety is stabilized in compounds 1 and 2 because of extended electron delocalization via participation of the appropriate metal orbital(s).

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Manganese(II) Semiquinonato and Manganese(III) Catecholato Complexes with Tridentate Ligand: Modeling the Substrate‐Binding State of Manganese‐Dependent Catechol Dioxygenase and Reactivity with Molecular Oxygen

Cited by 9 publications

References 90 publications

Five-coordinate M^II-semiquinonate (M = Fe, Mn, Co) complexes: reactivity models of the catechol dioxygenases

Five-coordinate M^II-semiquinonate (M = Fe, Mn, Co) complexes: reactivity models of the catechol dioxygenases

Rearrangements of organic peroxides and related processes

Ligand-Induced Tuning of the Oxidase Activity of μ-Hydroxidodimanganese(III) Complexes Using 3,5-Di-tert-butylcatechol as the Substrate: Isolation and Characterization of Products Involving an Oxidized Dioxolene Moiety

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Manganese(II) Semiquinonato and Manganese(III) Catecholato Complexes with Tridentate Ligand: Modeling the Substrate‐Binding State of Manganese‐Dependent Catechol Dioxygenase and Reactivity with Molecular Oxygen

Cited by 9 publications

References 90 publications

Five-coordinate MII-semiquinonate (M = Fe, Mn, Co) complexes: reactivity models of the catechol dioxygenases

Five-coordinate MII-semiquinonate (M = Fe, Mn, Co) complexes: reactivity models of the catechol dioxygenases

Rearrangements of organic peroxides and related processes

Ligand-Induced Tuning of the Oxidase Activity of μ-Hydroxidodimanganese(III) Complexes Using 3,5-Di-tert-butylcatechol as the Substrate: Isolation and Characterization of Products Involving an Oxidized Dioxolene Moiety

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Five-coordinate M^II-semiquinonate (M = Fe, Mn, Co) complexes: reactivity models of the catechol dioxygenases

Five-coordinate M^II-semiquinonate (M = Fe, Mn, Co) complexes: reactivity models of the catechol dioxygenases