ISBN: 978-83-60043-10-3 - eurobic9

Eurobic9, 2-6 September, 2008, Wrocław, Poland
P80. Synthesis and Characterization of N3-type Copper(II) Complex with
Calix[6]arene Upper Rim
T. Higa, T. Fujii, Y. Kajita, T. Inomata, Y. Funahashi, T. Ozawa, H. Masuda
Department of Materials Science and Engineering, Graduate School of Engineering, Nagoya Institute of
Technology, Showa-ku, Nagoya 466-8555, Japan
Dopamine β-monooxygenase (DβM) and peptidylglycine-α-hydroxylating monooxygenase (PHM) are two
mononuclear uncoupled copper-containing enzymes which catalyze essential hydroxylation reactions of
substrates by activating dioxygen. We previously synthesized their biomimetic model copper(II) complexes with
dipyridylamine-type ligands.[1] Addition of hydrogen peroxide to the solution containing the copper(II)
complex, [Cu(bpba)(MeOH)](ClO4)2 (bpba = bis(2-pyridylmethyl)tert-butylamine) generates copperhydroperoxide
species.[1] The reaction of the hydroperoxo species with dimethyl sulfide has exhibited catalytic
oxidation of dimethyl sulfide to dimethyl sulfoxide.[1] We introduce a calixarene group into the dipyridylaminetype
ligand as a cavity of encapsulating organic substrates nearby the reaction center, because increase in the
reaction probability is expected. In this study, we desgined a novel calixarene derivative, CA[6]BPA(Figure 1),
and synthesized the novel copper(II) and palladium(II) complexes. We will also discuss characterization of these
complexes and encapsulation of substrates by 1 H NMR measurements.
Acknowledgment: We gratefully acknowledge the support of this work by grants for overseas investigation
research from Tatematsu Foundation.
References:
[1] T. Fujii, A. Naito, S. Yamaguchi, A. Wada, Y. Funahashi, K. Jitsukawa, S. Nagatomo, T. Kitagawa, and
H. Masuda, Chem. Commun. 2003, 2700-2701.
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