本研究合成具有π-鍵結能力的含雙苯咪唑三牙基配子：雙苯咪唑-2-氧丙烷(bbmo)。合成了四個錯合物：[Cu(bbmo)(py)2](ClO4)2、[Cu(bbmo)(γ-pic)2](ClO4)2(CH3CN)、[Cu(bbmo)(2-acpy)](ClO4)2
(H2O)0.5及[Cu(bbmo)(nmim)2](ClO4)2。其中吡啶(py)、4-甲基吡啶(γ-pic)、2-乙醯基吡啶(2-acpy)及N-甲基咪唑(nmim)均是單牙配子。根據紅外光光譜、電子順磁共振光譜、電子吸收光譜及可見光光譜高斯交疊解析等，來探討二價銅錯合物的結構及鍵結的性質。此類錯合物為四角錐形體或拉長八面體，其中bbmo呈面形配位，py及γ-picoline的環面均垂直於配位的四角面。
由錯合物的可見光光譜高斯解析結果，得知二價銅錯合物結構的d軌域分佈順序為：
dxy ＞＞ dz2 > dx2-y2 ＞ dyz ＞ dxz
綜合本研究結果：所合成的含雙苯咪唑三牙基配子bbmo為π-donor的配位基。
[Cu(bbmo)(py)2](ClO4)2及[Cu(bbmo)(γ-pic)2](ClO4)2(CH3CN)為多種催化氧化反應的催化劑：
(一)具有酪胺酸酶的催化能力，能有效地在室溫下催化3,5-雙第三丁基
鄰苯二酚及2,4-雙第三丁基苯酚與氧氣的反應，形成3,5-雙第三丁基
雙醌。
(二)在室溫下具有催化苯甲氧化鋰(Lithium benzyloxide)與氧的反應，
形成苯甲醛(benzaldehyde)。
(三)推斷其反應過程中二價銅錯合物可能形成μ-η2：η2-peroxo
dicopper(II)及bis(μ-oxo)dicopper(Ⅲ)的結構，具有硫氧化反應
的催化能力。

Copper(II) complexes of bis(benzimidazol-2-yl)-2-oxopropane (bbmo), [Cu(bbmo)(py)2](ClO4)2, [Cu(bbmo)(γ-pic)2](ClO4)2(CH3CN), [Cu(bbmo)(2-acpy)](ClO4)2(H2O)0.5, and [Cu(bbmo)(nmim)2](ClO4)2, where py=pyridine, γ-pic=4-methylpyridine, 2-acpy=2-acetylpyridine, and nmim= 4-methylimidazole, have been synthesized, and characterized by elemental analyses, infrared, electronic absorption, and EPR spectroscopic measurements. These complexes are either five coordinated square pyramidal or six coordinated elongated octahedral structures, with a facially bonded bbmo. Both py and γ-pic nuclei are perpendicular to the main coordination plane.
Based on Gaussian analyses of the component bonds of the visible electronic spectra for these copper(II) complexes, the sequences of the d orbitals have been assigned as dxy ＞＞ dz2 > dx2-y2 ＞ dyz ＞ dxz for the elongated Oh or square pyramidal complexes. In conclusion, the bbmo tridentate ligand binds to copper d orbitals as a π-donor.
Both [Cu(bbmo)(py)2]2+ and [Cu(bbmo)(γ-pic)2]2+ exhibit excellent catalytic capabilities in some oxidation reactions. First, as tyrosinase, both 3,5-di-t-butylcatechol and 2,4-di-t-butylphenol are oxidized by O2 forming 3,5-di-t-butylquinone; secondly, the oxidation of lithium benzyloxide by O2 forms benzaldehyde; and thirdly, the oxidation of thioanisole by O2 results in the forming of methyl phenyl sulfoxide. It is likely that the catalytic species are either μ-η2：η2-peroxo dicopper(II) or bis(μ-oxo)dicopper(Ⅲ) complexes.

1、(a)Kitajima, N.; Fujisawa, K.; Moro-oka, Y.; Toriumi, K. J.
Am. Chem. Soc., 1989, 111, 8975. (b) Kitajima, N. ;
Fujisawa, K.; Moro-oka, Y.; Hashimoto, S.; Kitajima, T.;
Toriumi, K.; Tataumi, K.; Nakamura, A. J. Am. Chem.
Soc.,1992, 114, 1277.
2、Magus, K. A.; Ton-That, H.; Carpenter, J. E. in Bioinorganic
Chenistry of Copper, Kalin, K. D.; Tyeklar, Z. Eds., Chapman
& Hall, New York, 1993, pp143-150.
3、Sorrell, T. N.; Allen, W. E.; White, P. S. Inorg. Chem.,
1995, 34, 952.
4、Pidcock, E.; DeBeer, S.; Obias, H. V.; Hedman, B.; Hodgson,
K. D.; Karlin, K. D.; Solomom, E. I. J. Am. Chem. Soc.,1999,
121, 1870.
5、(a)Tolman, W. B. Acc, Chem. Rec., 1997, 30, 227. (b)Cahoy,
J.; Holland, P. L.; Tolman, W. B. Inorg. Chem., 1999, 38,
2162.
6、Holland, P. L.; Tolman, W. B. Coord. Chem. Rev., 1999, 190-
192, 855.
7、Casella, L.; Monzani, E.; Gullotti, M.; Cavagnino, D. Cerina
G.; Santagostini, L.; Ugo, R. Inorg. Chem. 1996, 35, 7516.
8、Casella, L.; Gullotti, M.; Radaelli, R.; Di Gennaro, P. J.
Chem. Soc .Chem. Commun, 1991, 1611.
9、Dagdigian, J. V.; Mckee, V., Reed, C. A. Inorg Chem, 1982,
21, 1332.
10、Purcell, K. F.; Kotz, J. C., in Inorganic Chemistry,
Saunders, W. B. Philadelphia, 1977.
11、Cornilsen, B.; Nakamoto, K. J. Inorg. Nucl. Chem.,1974, 36,
2467.
12、Saito, Y.; Takemoto, J.; Hutchinson, B.; Nakamoto, K.
Inorg. Chem., 1970, 11, 2003.
13、Hathway, B. J.; Billing, D. E., Coord. Chem. Rev., 1970, 5,
143.
14、Wilde, R. E.; Sirnivasan, T. K. J. Inorg. Nucl. Chem.,1974,
36, 323.
15、Hathaway, B. J.; Underhill, A. B. J. Chem. Soc., 1961, 3091.
16、Meek, D. W.; Ehrhardt, S. A. Inorg. Chem., 1965, 4, 584.
17、Su, C. -C.; Lin, Y. -L.; Wang, S. -L.; Chou, W. -C.
Transition Met. Chem., 1993, 18,113-117
18、Kroneck, P. M. H.; Vortisch, V.; Hemmerich, P. Eur. J. Bio.
Chem., 1980, 109, 603.
19、Jiang, F.; McCracken, J.; Peisach, J. J. Am. Chem. Soc.,
1990, 112, 9035.
20、Belford, R. L.; Calvin, M.; Belford, G. J. Chem. Phys.,
1957, 26, 1165.
21、Su, C. -C.; Lin, Y. -L.; Liu, S. -J. Polyhedron, 1993, 12,
2687.
22、Casella, L.; Monzani, E. Inorg. Chem.,1996, 35, 7516.
23、Taki, M.; Itoh, S.; Fukuzumi, S. J. Am. Chem. Soc., 2002,
124, 998.
24、蔡秀緣，國立台灣師範大學碩士論文，2002
25、黃錦松，國立台灣師範大學碩士論文，2002