Catalytic Performance of a Dicopper-Oxo Complex for Methane Hydroxylation

Yuta Hori, Yoshihito Shiota, Tomokazu Tsuji, Masahito Kodera, Kazunari Yoshizawa

研究成果: ジャーナルへの寄稿記事

5 引用 (Scopus)

抄録

A dicopper(II) complex, [Cu 2 (μ-OH)(6-hpa)] 3+ , where 6-hpa is 1,2-bis[2-[bis(2-pyridylmethyl)aminomethyl]-6-pyridyl]ethane, generates an oxyl radical of Cu II O and catalyzes the selective hydroxylation of benzene to phenol. From the structural similarity to methane activation catalysts (e.g., bare CuO + ion, Cu-ZSM-5, and particulate methane monooxygenase), it is expected to catalyze methane hydroxylation. The catalytic performance for the hydroxylation of methane to methanol by this dicopper complex is investigated by using density functional theory (DFT) calculations. The whole reaction of the methane conversion involves two steps without radical species: (1) C-H bond dissociation of methane by the Cu II O moiety and (2) C-O bond formation with methyl migration. In the first step, the activation barrier is calculated to be 10.2 kcal/mol, which is low enough for reactions taking place under normal conditions. The activation barrier by the other Cu II O 2 moiety is higher than that by the Cu II O moiety, which should work to turn the next catalytic cycle. DFT calculations show that the dicopper complex has a precondition to hydroxylate methane to methanol. Experimental verification is required to look in detail at the reactivity of this dicopper complex.

元の言語英語
ページ(範囲)8-11
ページ数4
ジャーナルInorganic Chemistry
57
発行部数1
DOI
出版物ステータス出版済み - 1 2 2018

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Hydroxylation
Methane
methane
Chemical activation
methane monooxygenase
activation
Density functional theory
Methanol
methyl alcohol
Ethane
density functional theory
Phenol
Benzene
ethane
phenols
particulates
Ions
reactivity
benzene
Catalysts

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

これを引用

Catalytic Performance of a Dicopper-Oxo Complex for Methane Hydroxylation. / Hori, Yuta; Shiota, Yoshihito; Tsuji, Tomokazu; Kodera, Masahito; Yoshizawa, Kazunari.

:: Inorganic Chemistry, 巻 57, 番号 1, 02.01.2018, p. 8-11.

研究成果: ジャーナルへの寄稿記事

Hori, Yuta ; Shiota, Yoshihito ; Tsuji, Tomokazu ; Kodera, Masahito ; Yoshizawa, Kazunari. / Catalytic Performance of a Dicopper-Oxo Complex for Methane Hydroxylation. :: Inorganic Chemistry. 2018 ; 巻 57, 番号 1. pp. 8-11.
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abstract = "A dicopper(II) complex, [Cu 2 (μ-OH)(6-hpa)] 3+ , where 6-hpa is 1,2-bis[2-[bis(2-pyridylmethyl)aminomethyl]-6-pyridyl]ethane, generates an oxyl radical of Cu II O • and catalyzes the selective hydroxylation of benzene to phenol. From the structural similarity to methane activation catalysts (e.g., bare CuO + ion, Cu-ZSM-5, and particulate methane monooxygenase), it is expected to catalyze methane hydroxylation. The catalytic performance for the hydroxylation of methane to methanol by this dicopper complex is investigated by using density functional theory (DFT) calculations. The whole reaction of the methane conversion involves two steps without radical species: (1) C-H bond dissociation of methane by the Cu II O • moiety and (2) C-O bond formation with methyl migration. In the first step, the activation barrier is calculated to be 10.2 kcal/mol, which is low enough for reactions taking place under normal conditions. The activation barrier by the other Cu II O 2 • moiety is higher than that by the Cu II O • moiety, which should work to turn the next catalytic cycle. DFT calculations show that the dicopper complex has a precondition to hydroxylate methane to methanol. Experimental verification is required to look in detail at the reactivity of this dicopper complex.",
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