Synthesis and Characterization of Blue Copper Model Complexes.

Accession number;02A0304383
Title;Synthesis and Characterization of Blue Copper Model Complexes.
Author; FUJISAWA KIYOSHI (Univ. of Tsukuba) MATSUNAGA YUKI (Univ. of Tsukuba) MIYASHITA YOSHITARO (Univ. of Tsukuba) YAMADA YASUNORI (Univ. of Tsukuba) OKAMOTO KEN'ICHI (Univ. of Tsukuba)
Journal Title;Abstracts. Symposium on Biofunctional Chemistry
Journal Code:L0836A
ISSN:
VOL.16th;NO.;PAGE.54-55(2001)
Figure&Table&Reference;
Pub. Country;Japan
Language;Japanese
Abstract;Blue copper proteins are electron carriers in biological systems. Because of their unusual spectral features including EPR and UV-Vis, the active site structures of this class of proteins have received considerable attention for a long time. This unique active site structure is generally believed to be associated with the function of blue copper proteins: high redox potentials and fast electron-transfer rates. In order to shed light on the detailed electric structural information using small molecule model compounds, we synthesized the thiolato complexes containing hindered tripodal ligands. Four-coordinate thiolato copper(II) complexes were prepared by the reaction of bis-.MU.-hydroxo complex with C6F5SH or Ph3CSH at low temperature, respectively. Another four-coordinate thiolato complex was also prepared by the reaction of mononuclear copper(II) hydroxo complex with CF3CH2SH. The structures were characterized by X-ray crystallography. All the four-coordinate copper(II) complexes closely mimic the striking spectroscopic characteristics of blue copper proteins. Furthermore, five-coordinate thiolato copper(II) complex was also prepared by the reaction of bis-.MU.-hydroxo complex with 2-mercapto-1-methylimidazole at low temperature. Their physicochemical properties as well as .MU.-.ETA.2:.ETA.2-disulfido copper(II) complex will be presented in detail. (author abst.)