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

Eurobic9, 2-6 September, 2008, Wrocław, Poland
P125. Effect of the Dihedral Angles of Two CuS2 Planes of µ-η 2 :η 2 -
Disulfidodicopper(II) Complexes on Their Reactivities
J. Matsumoto a , Y. Kajita a , Y. Wasada-Tsutsui b , I. Takahashi c , S. Hirota c , Y. Funahashi a ,
T. Ozawa a , H. Masuda a
a
Materials Science and Engineering, Nagoya Institute of Technology, Showa-ku, Nagoya, 466-8555, Aichi, Japan
e-mail: 19415166@stn.nitech.ac.jp
b
Graduate School of Natural Sciences, Nagoya City University, Mizuho-ku, Nagoya, 467-8501, Aichi, Japan
c
Graduate School of Materials Science, Nara Institute of Science and Technology, Takayama-cho, Ikoma, 630-0192,
Nara, Japan
A new focus of interest in copper-sulfur coordination chemistry is derived from the recent discovery of
a tetracopper-sulfur cluster at the CuZ active sites of nitrous oxide reductase that catalyzes the terminal step in
bacterial denitrification.
We newly synthesized three µ-η 2 :η 2 -disulfidodicopper(II) complexes with cis, cis-1, 3, 5-triaminocyclohexane
derivatives (Figure 1), which were characterized in detail by elemental, electrochemical, and X-ray structure
analyses, and electronic absorption, IR, ESI mass, and resonance Raman spectroscopic methods. In this study,
we found that their reactivities with exogenous substrates are related to the dihedral angles defined by two CuS2
planes.[1] This finding was also examined from the DFT calculation of the two complexes with bent and planar
Cu2S2 structures. The atomic charges on Cu and S atom were localized when the dihedral angles were decreased;
1.137, -0.470 for the bent one and 1.107, -0.450 for the planar one, respectively. These results indicate that the
reactivities of disulfidodicopper(II) complexes depend upon the nucleophilicities of S atoms affected by the
localized charge.
References:
[1] Y. Kajita, J. Matsumoto, I. Takahashi, S. Hirota, Y. Funahashi, T. Ozawa, and H. Masuda, Eur. J. Inorg.
Chem. accepted.
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