Photoinduced radical chain reactions between alkylcobalt(III) complexes and iodine

Kunio Ishikawa, Shunichi Fukuzumi, Tatsushi Goto, Toshio Tanaka

研究成果: ジャーナルへの寄稿記事

3 引用 (Scopus)

抄録

Cobalt-carbon bonds of various alkylcobalt(III) complexes, cis-[CoR 2 (bipy) 2 ]ClO 4 (R = Me, Et, or PhCH 2 ; bipy = 2,2′-bipyridine), trans-[CoMe 2 (L)] (L = 3,9-dimethyl-4,8-diazaundeca-3,8-diene-2,10-dione dioximate), and [CoR(Hdmg) 2 (py)] (R = Me or Et; Hdmg = dimethylglyoximate; py = pyridine), are readily cleaved by iodine in carbon tetrachloride to yield alkyl iodides via photoinduced radical chain reactions with large quantum yields (e.g. Φ = 7.0 × 10 3 ) under low-energy irradiation (λ 517 nm). The rate-determining step in the radical chain reactions is suggested to be electron transfer from alkylcobalt(III) complexes to iodine atoms (I . ) which are produced by the photodissociation of I 2 , based on the formation of by-products that could arise only via electron-transfer processes as well as the kinetic comparison between alkylcobalt(III) complexes and tetra-alkyltin compounds.

元の言語英語
ページ(範囲)85-90
ページ数6
ジャーナルJournal of the Chemical Society, Dalton Transactions
発行部数1
DOI
出版物ステータス出版済み - 12 1 1990
外部発表Yes

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Iodine
Photodissociation
Electrons
Carbon Tetrachloride
Iodides
Quantum yield
Cobalt
Byproducts
Carbon
Irradiation
Atoms
Kinetics
pyridine

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

これを引用

Photoinduced radical chain reactions between alkylcobalt(III) complexes and iodine. / Ishikawa, Kunio; Fukuzumi, Shunichi; Goto, Tatsushi; Tanaka, Toshio.

:: Journal of the Chemical Society, Dalton Transactions, 番号 1, 01.12.1990, p. 85-90.

研究成果: ジャーナルへの寄稿記事

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abstract = "Cobalt-carbon bonds of various alkylcobalt(III) complexes, cis-[CoR 2 (bipy) 2 ]ClO 4 (R = Me, Et, or PhCH 2 ; bipy = 2,2′-bipyridine), trans-[CoMe 2 (L)] (L = 3,9-dimethyl-4,8-diazaundeca-3,8-diene-2,10-dione dioximate), and [CoR(Hdmg) 2 (py)] (R = Me or Et; Hdmg = dimethylglyoximate; py = pyridine), are readily cleaved by iodine in carbon tetrachloride to yield alkyl iodides via photoinduced radical chain reactions with large quantum yields (e.g. Φ = 7.0 × 10 3 ) under low-energy irradiation (λ 517 nm). The rate-determining step in the radical chain reactions is suggested to be electron transfer from alkylcobalt(III) complexes to iodine atoms (I . ) which are produced by the photodissociation of I 2 , based on the formation of by-products that could arise only via electron-transfer processes as well as the kinetic comparison between alkylcobalt(III) complexes and tetra-alkyltin compounds.",
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N2 - Cobalt-carbon bonds of various alkylcobalt(III) complexes, cis-[CoR 2 (bipy) 2 ]ClO 4 (R = Me, Et, or PhCH 2 ; bipy = 2,2′-bipyridine), trans-[CoMe 2 (L)] (L = 3,9-dimethyl-4,8-diazaundeca-3,8-diene-2,10-dione dioximate), and [CoR(Hdmg) 2 (py)] (R = Me or Et; Hdmg = dimethylglyoximate; py = pyridine), are readily cleaved by iodine in carbon tetrachloride to yield alkyl iodides via photoinduced radical chain reactions with large quantum yields (e.g. Φ = 7.0 × 10 3 ) under low-energy irradiation (λ 517 nm). The rate-determining step in the radical chain reactions is suggested to be electron transfer from alkylcobalt(III) complexes to iodine atoms (I . ) which are produced by the photodissociation of I 2 , based on the formation of by-products that could arise only via electron-transfer processes as well as the kinetic comparison between alkylcobalt(III) complexes and tetra-alkyltin compounds.

AB - Cobalt-carbon bonds of various alkylcobalt(III) complexes, cis-[CoR 2 (bipy) 2 ]ClO 4 (R = Me, Et, or PhCH 2 ; bipy = 2,2′-bipyridine), trans-[CoMe 2 (L)] (L = 3,9-dimethyl-4,8-diazaundeca-3,8-diene-2,10-dione dioximate), and [CoR(Hdmg) 2 (py)] (R = Me or Et; Hdmg = dimethylglyoximate; py = pyridine), are readily cleaved by iodine in carbon tetrachloride to yield alkyl iodides via photoinduced radical chain reactions with large quantum yields (e.g. Φ = 7.0 × 10 3 ) under low-energy irradiation (λ 517 nm). The rate-determining step in the radical chain reactions is suggested to be electron transfer from alkylcobalt(III) complexes to iodine atoms (I . ) which are produced by the photodissociation of I 2 , based on the formation of by-products that could arise only via electron-transfer processes as well as the kinetic comparison between alkylcobalt(III) complexes and tetra-alkyltin compounds.

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