Reaction of Cu(I) complexes bearing a phenol group in the ligand with O2

Shinobu Itoh; Yasuji Hashimoto; Shunichi Fukuzumi

doi:10.1016/S0926-860X(99)00391-9

Reaction of Cu(I) complexes bearing a phenol group in the ligand with O₂

Shinobu Itoh, Yasuji Hashimoto, Shunichi Fukuzumi

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

Reactions of dioxygen and Cu(I) complexes of a series of bis[2-(2-pyridyl)ethyl]amine ligands bearing different phenol groups (2H = N,N-bis[2-(2-pyridyl)ethyl]-2- (3-hydroxyphenyl)ethylamine, 3H = N,N-bis[2- (2-pyridyl)ethyl]tyramine, 4H = N,N-bis[2- (2-pyridyl)ethyl]-2-(2-hydroxy-5-methylphenyl)ethylamine) have been investigated to obtain insight into the reactivity of copper-active oxygen complexes toward phenols. Treatment of [Cu^I(2H)](PF₆) and [Cu^I(3H)](PF₆) with O₂ resulted in the benzylic ligand hydroxylation in 9 and 14%, respectively, together with formation of polymeric products, while the reaction of [Cu^I(4H)](PF₆) and O₂ gave a dinuclear phenolate copper(II) complex, [Cu₂^II(4^-)₂]²⁺, and H₂O₂. The structure and reactivity of the active oxygen intermediates are discussed.

Original language	English
Pages (from-to)	453-461
Number of pages	9
Journal	Applied Catalysis A: General
Volume	194
DOIs	https://doi.org/10.1016/S0926-860X(99)00391-9
State	Published - 13 Mar 2000

Bibliographical note

Funding Information:
The present study was financially supported in part by a Grant-in-Aid for Scientific Research on Priority Area (Molecular Biometallics: 10129218 and 11116219; Electrochemistry of Ordered Interface: 10131242 and 11118244) from the Ministry of Education, Science, Sports, and Culture of Japan.

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10.1016/S0926-860X(99)00391-9

Cite this

@article{246a4c745be346fe93b96791220c0122,

title = "Reaction of Cu(I) complexes bearing a phenol group in the ligand with O2",

abstract = "Reactions of dioxygen and Cu(I) complexes of a series of bis[2-(2-pyridyl)ethyl]amine ligands bearing different phenol groups (2H = N,N-bis[2-(2-pyridyl)ethyl]-2- (3-hydroxyphenyl)ethylamine, 3H = N,N-bis[2- (2-pyridyl)ethyl]tyramine, 4H = N,N-bis[2- (2-pyridyl)ethyl]-2-(2-hydroxy-5-methylphenyl)ethylamine) have been investigated to obtain insight into the reactivity of copper-active oxygen complexes toward phenols. Treatment of [CuI(2H)](PF6) and [CuI(3H)](PF6) with O2 resulted in the benzylic ligand hydroxylation in 9 and 14%, respectively, together with formation of polymeric products, while the reaction of [CuI(4H)](PF6) and O2 gave a dinuclear phenolate copper(II) complex, [Cu2II(4-)2]2+, and H2O2. The structure and reactivity of the active oxygen intermediates are discussed.",

author = "Shinobu Itoh and Yasuji Hashimoto and Shunichi Fukuzumi",

note = "Funding Information: The present study was financially supported in part by a Grant-in-Aid for Scientific Research on Priority Area (Molecular Biometallics: 10129218 and 11116219; Electrochemistry of Ordered Interface: 10131242 and 11118244) from the Ministry of Education, Science, Sports, and Culture of Japan.",

year = "2000",

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doi = "10.1016/S0926-860X(99)00391-9",

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T1 - Reaction of Cu(I) complexes bearing a phenol group in the ligand with O2

AU - Itoh, Shinobu

AU - Hashimoto, Yasuji

AU - Fukuzumi, Shunichi

N1 - Funding Information: The present study was financially supported in part by a Grant-in-Aid for Scientific Research on Priority Area (Molecular Biometallics: 10129218 and 11116219; Electrochemistry of Ordered Interface: 10131242 and 11118244) from the Ministry of Education, Science, Sports, and Culture of Japan.

PY - 2000/3/13

Y1 - 2000/3/13

N2 - Reactions of dioxygen and Cu(I) complexes of a series of bis[2-(2-pyridyl)ethyl]amine ligands bearing different phenol groups (2H = N,N-bis[2-(2-pyridyl)ethyl]-2- (3-hydroxyphenyl)ethylamine, 3H = N,N-bis[2- (2-pyridyl)ethyl]tyramine, 4H = N,N-bis[2- (2-pyridyl)ethyl]-2-(2-hydroxy-5-methylphenyl)ethylamine) have been investigated to obtain insight into the reactivity of copper-active oxygen complexes toward phenols. Treatment of [CuI(2H)](PF6) and [CuI(3H)](PF6) with O2 resulted in the benzylic ligand hydroxylation in 9 and 14%, respectively, together with formation of polymeric products, while the reaction of [CuI(4H)](PF6) and O2 gave a dinuclear phenolate copper(II) complex, [Cu2II(4-)2]2+, and H2O2. The structure and reactivity of the active oxygen intermediates are discussed.

AB - Reactions of dioxygen and Cu(I) complexes of a series of bis[2-(2-pyridyl)ethyl]amine ligands bearing different phenol groups (2H = N,N-bis[2-(2-pyridyl)ethyl]-2- (3-hydroxyphenyl)ethylamine, 3H = N,N-bis[2- (2-pyridyl)ethyl]tyramine, 4H = N,N-bis[2- (2-pyridyl)ethyl]-2-(2-hydroxy-5-methylphenyl)ethylamine) have been investigated to obtain insight into the reactivity of copper-active oxygen complexes toward phenols. Treatment of [CuI(2H)](PF6) and [CuI(3H)](PF6) with O2 resulted in the benzylic ligand hydroxylation in 9 and 14%, respectively, together with formation of polymeric products, while the reaction of [CuI(4H)](PF6) and O2 gave a dinuclear phenolate copper(II) complex, [Cu2II(4-)2]2+, and H2O2. The structure and reactivity of the active oxygen intermediates are discussed.

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