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Synthesis and reactivity of (μ-η 2 :η 2 -peroxo)dicopper(II) complexes with dinucleating ligands: Hydroxylation of xylyl linker with a NIH shift

Journal of Organometallic Chemistry, ISSN: 0022-328X, Vol: 692, Issue: 1, Page: 111-121
2007
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  • Citations
    11
    • Citation Indexes
      11
  • Captures
    12

Article Description

New hexadentate dinucleating ligands having a xylyl linker, X–L–R, were synthesized, where X–L–R = 1,3-bis[bis(6-methyl-2-pyridylmethyl)aminomethyl]-2,4,6-trimethybenzene (Me 2 –L–Me) and 1,3-bis[bis(6-methyl-2-pyridylmethyl)aminomethyl]-2-fluorobenzene (H–L–F). They form dinuclear copper(I) complexes, [Cu 2 (X–L–R)] 2+ (Me 2 –L–Me ( 1 ) and H–L–F ( 2 )). The copper(I) complexes in acetone at −78 °C react with O 2 to produce intra- and intermolecular (μ-η 2 :η 2 -peroxo)dicopper(II) species depending on the concentrations of the complexes: both complexes generate intramolecular (μ-η 2 :η 2 -peroxo)dicopper(II) species [Cu 2 (O 2 )(X–L–R)] 2+ ( 1 -O 2 and 2 -O 2 ) at the concentrations below ∼5 mM, whereas at ∼60 mM, both complexes produce intermolecular (μ-η 2 :η 2 -peroxo)dicopper(II) species, which were confirmed by the electronic and resonance Raman spectroscopies. The electronic spectrum of 1 -O 2 in acetone at concentrations below ∼5 mM showed an absorption band at ( λ max = 442 nm, ε = 5600 M −1 cm −1 ) assignable to the πσ∗ (O–O)-to-Cu(II) ( (dx2-y2+dx2-y2) component) LMCT transition in addition to an intense band attributable to the πσ∗ (O–O)-to-Cu(II) ( (dx2-y2-dx2-y2) component) LMCT transition ( λ max = 359 nm, ε = 21000 M −1 cm −1 ), indicating that the (μ-η 2 :η 2 -peroxo)Cu(II) 2 core of 1 -O 2 takes a butterfly structure. Decomposition of 1 -O 2 resulted in hydroxylation of the 2-position of the xylyl linker with 1,2-methyl migration (NIH shift), suggesting that the hydroxylation reaction proceeds via a cationic intermediate as proposed for closely related (μ-η 2 :η 2 -peroxo)Cu(II) 2 complexes having a xylyl linker. Kinetic study of the decomposition (hydroxylation of the xylyl linker) of 1 -O 2 suggests that a stereochemical effect of the methyl group in the 2-position of the xylyl linker has a significant influence on a transition state for decomposition (hydroxylation of the xylyl linker).

Bibliographic Details

Takahiro Matsumoto; Hideki Furutachi; Shigenori Nagatomo; Takehiko Tosha; Shuhei Fujinami; Teizo Kitagawa; Masatatsu Suzuki

Elsevier BV

Biochemistry, Genetics and Molecular Biology; Chemistry; Materials Science

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