銅蛋白質模型錯合物研究：雙(2啶甲基)醚之銅錯合物的合成、結構及性質研究

陳筱嵐(Hsiao-Lan Chen)

指導教授 ： 蘇展政博士

國立臺灣師範大學/理學院/化學系/碩士(2002年)

摘要

無資料

關鍵字

高斯交疊解析 ； p-acceptor配位基 ； 2,4-二-特-丁基苯酚 ； 催化氧化

並列摘要

Abstract
Four types of copper(II) complexes of bis(2-pyridylmethyl)ether
(bpmo) have been prepared.
(1)[Cu(bpmo)(NN)](ClO4)2, where NN stands for 2,2’-bipyridine (bipy), 1,10-phenanthroline (phen), and N,N,N’,N’-tetramethylethylene-
diamine (tmen).
(2)[Cu(bpmo)(N)](ClO4)2, where N represents 4-methylpyridine (4Mepy), N-methylimidazole (NMeIm), and 2-(Hydroxymethyl)pyridine
(pyCH2OH).
(3)[Cu(bpmo)(X)2], where X is Br and Cl.
(4)[Cu(bpmo)2](ClO4)2.
These complexes have been characterized by elemental analyses, IR, UV-VIS, and EPR spectroscopic measurements, and single-crystal X-ray diffraction. The crystal data of the complexes are described below:
(a) fac-[Cu(bpmo)(bipy)(ClO4)](ClO4)
Triclinic, space group P-1, a = 8.8186(1)Å, b = 10.6142(2)Å, c = 15.0084(4)Å, a = 88.644(1)º, b = 75.102(1)º, g = 67.897(2)º, Z = 2, R = 0.047, Rw = 0.090.
(b) fac-[Cu(bpmo)(phen)](ClO4)2
Monoclinic, space group C2/m, a = 19.0002(4)Å, b = 10.9264(3)Å, c = 16.8516(4)Å, a = 90.00º, b = 117.310(2)º, g = 90.00º, Z = 4, R = 0.141, Rw = 0.267.
(c) fac-[Cu(bpmo)(tmen)(CH3CN)](ClO4)2(CH3CN)
Monoclinic, space group P21/n, a = 8.308(2)Å, b = 17.208(5)Å, c = 21.242(8)Å, a = 90.00º, b = 100.07(3)º, g = 90.00º, Z = 4, R = 0.110, Rw =0.312.
(d) mer-[Cu(bpmo)(4Mepy)(ClO4)](ClO4)(H2O)
Triclinic, space group P-1, a = 8.3778(1)Å, b = 8.6333(2)Å, c = 18.3404(5)Å, a = 76.641(1)º, b = 83.815(1)º, g = 62.407(1)º, Z = 2, R = 0.102, Rw = 0.256.
(e) mer-[Cu(bpmo)(NMeIm)(ClO4)](ClO4)
Triclinic, space group P-1, a = 8.388(8)Å, b = 8.693(3)Å, c = 16.599(3)Å, a = 78.58(2)º, b = 82.68(5)º, g = 62.86(5)º, Z = 2, R = 0.064, Rw = 0.066.
(f) mer-[Cu(bpmo)(Br)2]
Monoclinic, space group P21/n, a = 8.2448(2)Å, b = 12.8300(3)Å, c = 13.1692(4)Å, a = 90.00º, b = 92.4581(11)º, g = 90.00º, Z = 4, R = 0.049, Rw = 0.102.
(g) mer-[Cu(bpmo)(Cl)2]
Monoclinic, space group P21/n, a = 8.1618(2)Å, b = 12.5669(3)Å, c = 12.8289(4)Å, a = 90.00º, b = 91.622(1)º, g = 90.00º, Z = 4, R = 0.031, Rw = 0.063.
Based on Gaussian analyses of the solution LF spectra of the type (1) and (2) complexes, the bpmo binds to copper as a p-acceptor.
The reactions of O2 with the Cu(I) complex, [Cu(bpmo)]+, at room temperature have been investigated. The reaction of 2,4-di-tert-butyl-
phenol with O2 in the presence of [Cu(bpmo)]+ yields the dimeric product, 3,3¢,5,5¢-tetra-tert-butyl-2,2¢-biphenol, suggesting the formation of the bis(m-oxo)dicopper(Ⅲ) intermediate.

並列關鍵字

Gaussian analyses ； p-acceptor ligand ； 2,4-di-tert-butyl-phenol ； catalytic oxidation

參考文獻

64. 蘇展政，吳秋月 化學 1996, 54, 57.

1. Volbeda, A.; Hol, W. G. J. J. Mol. Biol. 1989, 206, 531.

4. Solomon, E. I.; Chen, P.; Metz, M.; Palmer. A.; Lee, S-K. Angew. Chem. Int. Ed. 2001, 40, 4570.

12. Cahoy, J.; Holland, P. L.; Tolman, W. B. Inorg. Chem. 1999, 38, 2161.

27. Que, L., Jr.; Tolman, W. B. Angew. Chem. Int. Ed. 2002, 41, 1114.