Theoretical Study on the Aliphatic <scp>C─H</scp> Bond Activation by a Mononuclear Manganese(<scp>III</scp>) Iodosylbenzene Complex

Jeong, Donghyun; Hirao, Hajime; Cho, Jaeheung

doi:10.1002/bkcs.12300

Cited by 5 publications

(3 citation statements)

References 38 publications

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“… Therefore, in the hydrocarbon oxidation reaction, 3 performed rate-determining C–H bond activation of the substrates (R′–H), affording the Mn(III)–(OH 2 )(OCH 2 CF 3 ) adduct with R′ • . The subsequent step is the electron transfer from R′ • to Mn(III) species to form the Mn(II) species, which reacts with 3 to produce the Mn(III)–(OCH 2 CF 3 ) 2 species, and the formed R′ + is converted to the products. , It should be noted that anthrone and anthraquinone are major products in the reaction of 3 and DHA (Table S13). Anthracene, which is the two-electron-oxidized product of DHA, can be further oxidized into anthrone or anthraquinone by a strong oxidant with high redox potential (see Scheme S1 for the oxidation reaction of DHA with 3 ) .…”

Section: Resultsmentioning

confidence: 99%

“…Fundamental biological oxidation processes such as the lipoxygenase-catalyzed reaction, metal-mediated O 2 activation, and oxygen evolution involve many critical reactive metal–oxygen intermediates. − Among the oxygen-coordinating metal complexes, high-valent manganese–hydroxide [Mn n + –(OH), where n ≥ 3] adducts have been assessed as reactive species in enzymatic oxidation reactions. − For example, Mn III –(OH) complexes have been employed as an active oxidant in lipoxygenases, which activate the C–H bond of polyunsaturated fatty acids by hydrogen atom abstraction. − Mn IV –(OH) species have often been proposed as intermediates in catalytic O 2 activation or O 2 production. − , …”

Section: Introductionmentioning

confidence: 99%

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Structure and Reactivity of Nonporphyrinic Terminal Manganese(IV)–Hydroxide Complexes in the Oxidative Electrophilic Reaction

Park

Kim

et al. 2022

Inorg. Chem.

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High-valent transition metal–hydroxide complexes have been proposed as essential intermediates in biological and synthetic catalytic reactions. In this work, we report the single-crystal X-ray structure and spectroscopic characteristics of a mononuclear nonporphyrinic MnIV–(OH) complex, [MnIV(Me3-TPADP)(OH)(OCH2CH3)]2+ (2), using various physicochemical methods. Likewise, [MnIV(Me3-TPADP)(OH)(OCH2CF3)]2+ (3), which is thermally stable at room temperature, was also synthesized and characterized spectroscopically. The MnIV–(OH) adducts are capable of performing oxidation reactions with external organic substrates such as C–H bond activation, sulfoxidation, and epoxidation. Kinetic studies, involving the Hammett correlation and kinetic isotope effect, and product analyses indicate that 2 and 3 exhibit electrophilic oxidative reactivity toward hydrocarbons. Density functional theory calculations support the assigned electronic structure and show that direct C–H bond activation of the MnIV–(OH) species is indeed possible.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Structure and Reactivity of Nonporphyrinic Terminal Manganese(IV)–Hydroxide Complexes in the Oxidative Electrophilic Reaction

Park

Kim

et al. 2022

Inorg. Chem.

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“…Iodosylarenes (ArIO) are most widely used as artificial oxidants in the generation of metal-oxo species as well as in catalytic oxidation of organic substrates. − Metal-iodosylarene adducts usually act as precursors of metal-oxo species, but they can also function as direct oxidants for organic substrates . However, compared to metal-oxo species, relatively few metal-iodosylarene complexes have been isolated. − These include those of Fe, , Mn, − and Co. , Most metal-iodosylarenes are rather weak oxidants; only an Fe(III)- and a Mn(III)-iodosylarene complex can activate strong C–H bonds. , …”

Section: Introductionmentioning

confidence: 99%

Structure and Reactivity of a Seven-Coordinate Ruthenium Iodosylbenzene Complex

et al. 2023

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Seven-coordinate (CN7) ruthenium-oxo species have attracted much attention as highly reactive intermediates in both organic and water oxidation. Apart from metal-oxo, other metal-oxidant adducts, such as metal-iodosylarenes, have also recently emerged as active oxidants. We reported herein the first example of a CN7 Ru-iodosylbenzene complex, [RuIV(bdpm)(pic)2(O)I(Cl)Ph]+ (H2bdpm = [2,2′-bipyridine]-6,6′-diylbis(diphenylmethanol); pic = 4-picoline). The X-ray crystal structure of this complex shows that it adopts a distorted pentagonal bipyramidal geometry with Ru–O(I) and O–I distances of 2.0451(39) and 1.9946(40) Å, respectively. This complex is highly reactive, and it readily undergoes O-atom transfer (OAT) and C–H bond activation reactions with various organic substrates. This work should provide insights for the development of new highly reactive oxidizing agents based on CN7 geometry.

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Identification of a cobalt(IV)–oxo intermediate as an active oxidant in catalytic oxidation reactions

Malik

Lee

Nam

2022

Bulletin Korean Chem Soc

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We report the catalytic oxidation of organic substrates by a cobalt complex, [Co III (TAML)] À (TAML = tetra-amido macrocyclic ligand), and meta-chloroperbenzoic acid (m-CPBA) under the mild reaction conditions and the identification of a cobalt(IV)-oxo intermediate, [Co IV (TAML)(O)] 2À , as an active oxidant in the catalytic oxidation reactions. In the hydroxylation of cyclohexane, cyclohexanol is the sole product and the hydroxylation reaction occurs via an oxygen non-rebound mechanism. Kinetic isotope effect value of 3.1, obtained in the oxidation of cyclohexane-h 12 /d 12 , indicates that a hydrogen atom abstraction from cyclohexane by the cobalt(IV)-oxo complex is the rate-determining step. The catalytic oxidation of cyclohexene prefers the C═C bond epoxidation to the C-H bond activation, yielding cyclohexene oxide as a sole product. In the epoxidation of cis-and transstilbenes, cis-and trans-stilbene oxides, respectively, are yielded stereoselectively. The present study reports a highly selective catalytic oxidation of organic substrates by a cobalt complex and m-CPBA and the involvement of a cobalt(IV)-oxo intermediate as an active oxidant in the catalytic oxidation reactions.

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Theoretical Study on the Aliphatic C─H Bond Activation by a Mononuclear Manganese(III) Iodosylbenzene Complex

Cited by 5 publications

References 38 publications

Structure and Reactivity of Nonporphyrinic Terminal Manganese(IV)–Hydroxide Complexes in the Oxidative Electrophilic Reaction

Structure and Reactivity of Nonporphyrinic Terminal Manganese(IV)–Hydroxide Complexes in the Oxidative Electrophilic Reaction

Structure and Reactivity of a Seven-Coordinate Ruthenium Iodosylbenzene Complex

Identification of a cobalt(IV)–oxo intermediate as an active oxidant in catalytic oxidation reactions

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