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.
| Original language | English |
|---|---|
| Pages (from-to) | 8-11 |
| Number of pages | 4 |
| Journal | Inorganic Chemistry |
| Volume | 57 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - Jan 2 2018 |
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All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Inorganic Chemistry
Cite this
Catalytic Performance of a Dicopper-Oxo Complex for Methane Hydroxylation. / Hori, Yuta; Shiota, Yoshihito; Tsuji, Tomokazu; Kodera, Masahito; Yoshizawa, Kazunari.
In: Inorganic Chemistry, Vol. 57, No. 1, 02.01.2018, p. 8-11.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Catalytic Performance of a Dicopper-Oxo Complex for Methane Hydroxylation
AU - Hori, Yuta
AU - Shiota, Yoshihito
AU - Tsuji, Tomokazu
AU - Kodera, Masahito
AU - Yoshizawa, Kazunari
PY - 2018/1/2
Y1 - 2018/1/2
N2 - 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.
AB - 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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U2 - 10.1021/acs.inorgchem.7b02563
DO - 10.1021/acs.inorgchem.7b02563
M3 - Article
VL - 57
SP - 8
EP - 11
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 1
ER -