Aliphatic C-H bond activation initiated by a (μ-η2: η2-peroxo)dicopper(II) complex in comparison with cumylperoxyl radical

Takahiro Matsumoto, Kei Ohkubo, Kaoru Honda, Akiko Yazawa, Hideki Furutachi, Shuhei Fujinami, Shunichi Fukuzumi, Masatatsu Suzuki

研究成果: ジャーナルへの寄稿学術誌査読

52 被引用数 (Scopus)


A (μ-η22-peroxo)dicopper(II) complex, [Cu2(H-L)(O2)]2+ (1-O2), supported by the dinucleating ligand 1,3-bis[bis(6-methyl-2-pyridylmethyl)aminomethyl] benzene (H-L) is capable of initiating C-H bond activation of a variety of external aliphatic substrates (SHn): 10-methyl-9,10-dihydroacridine (AcrH2), 1,4-cyclohexadiene (1,4-CHD), 9,10-dihydroanthracene (9,10-DHA), fluorene, tetralin, toluene, and tetrahydrofuran (THF), which have C-H bond dissociation energies (BDEs) ranging from ∼75 kcal mol-1 for 1,4-CHD to ∼92 kcal mol-1 for THF. Oxidation of SH n afforded a variety of oxidation products, such as dehydrogenation products (SH(n-2)), hydroxylated and further-oxidized products (SH(n-1)OH and SH(n-2)=O), dimers formed by coupling between substrates (H(n-1)S-SH(n-1)) and between substrate and H-L (H-L-SH(n-1)). Kinetic studies of the oxidation of the substrates initiated by 1-O2 in acetone at -70°C revealed that there is a linear correlation between the logarithms of the rate constants for oxidation of the C-H bonds of the substrates and their BDEs, except for THF. The combination of this correlation and the relatively large deuterium kinetic isotope effects (KIEs), k2H/k2D (13 for 9,10-DHA, ≳29 for toluene, and ∼34 for THF at -70°C and ∼9 for AcrH2 at -94°C) indicates that H-atom transfer (HAT) from SHn (SDn) is the rate-determining step. Kinetic studies of the oxidation of SHn by cumylperoxyl radical showed a correlation similar to that observed for 1-O2, indicating that the reactivity of 1-O2 is similar to that of cumylperoxyl radical. Thus, 1-O 2 is capable of initiating a wide range of oxidation reactions, including oxidation of aliphatic C-H bonds having BDEs from ∼75 to ∼92 kcal mol-1, hydroxylation of the m-xylyl linker of H-L, and epoxidation of styrene (Matsumoto, T.; et al. J. Am. Chem. Soc. 2006, 128, 3874).

ジャーナルJournal of the American Chemical Society
出版ステータス出版済み - 7月 8 2009

!!!All Science Journal Classification (ASJC) codes

  • 触媒
  • 化学一般
  • 生化学
  • コロイド化学および表面化学


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