| Summary: | 碩士 === 國立臺灣師範大學 === 化學研究所 === 91 === Copper(Ⅱ) complexes containing N,N-bis(2-pyridylmethyl)-4'- methoxyaninline ( bpma ) or 1,1'-bi-2-naphthol ( binol ) have been synthesized , and characterized by element analysies, and UV-VIS and, IR , and EPR spectroscopic measurements. These copper(Ⅱ) complexes catalyze the sulfoxidation of thioanisole with hydrogen peroxide. The sulfoxidation products have been isolated by column chromatograph and identified by NMR.
By using three-dimensional X-ray diffraction methods, the crystal and molecular structures of the following complexes have been determined. The crystal data are given below:
1. fac-[Cu(bpma)(bipy)(ClO4)](ClO4)
Monoclinic, space group P 21/c , a = 17.462 (2) , b = 9.694 (1) , c = 17.911 (2) , β= 95.911(3) °, V = 2102.7(2) Å3, Z = 4, R = 0.041, Rw = 0.041。
2. mer-[Cu(bpma)(py)(ClO4)](ClO4)
Monoclinic, space group P 21/c , a = 15.732(4) , b = 32.164 (8), c = 10.725(3), β = 90.000(10) °, V = 5426.5 (24), Z = 8, R = 0.079, Rw = 0.085。
3. mer-[Cu(bbmemn)(py)(ClO4)](ClO4)
Triclinic, space group P -1, a = 12.8633(7), b = 14.219(8), c = 22.931 (1), α= 77.682 (1) °, β= 78.695 (1) °, γ= 84.351 (1) ° V = 4011.2(4), Z = 6, R = 0.077, Rw = 0.075。
The results of the study may be summarized into two categories:
1. The series of copper(II) complexes in this study are catalysts for the oxidation reactions analogous to those catalyzed by tyrosinase. In other words, -η2:η2-peroxo dicopper(II) or bis--oxo dicopper(III) intermediates are formed during the oxidation reactions of the copper complexes with bpma, bbmemn, bbms, bmimemt and bbprmo.
2. The copper(II) complexes, [Cu(L)(py)x](ClO4)2, where L stands for a bidentate or a tridentate ligand, can perform the catalytic sulfoxidation reaction at room temperature, as mixed with hydrogen peroxide. The results of sulfoxidation competition reactions, suggest that these series of copper(II) complexes proceed in an electrophilic catalytic sulfoxidation reaction.
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