研究生: |
曾秀燉 |
---|---|
論文名稱: |
N-乙醯乙醯甘胺酸二價銅錯合物之合成、光譜及鍵結性質研究 |
指導教授: | 蘇展政 |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
畢業學年度: | 85 |
語文別: | 中文 |
論文頁數: | 117 |
中文關鍵詞: | -乙醯乙醯甘胺酸 、二價銅錯合物 、光譜 |
論文種類: | 學術論文 |
相關次數: | 點閱:163 下載:0 |
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本研究以 N-乙醯乙醯甘胺酸 (naagH2) 為主要配子,合成了兩系列的錯合物,(1) [Cu(A)(NN)(H2O)] 和[Cu(A)(NN)(ClO4)],其中A為 (naag),NN 為 1,10-二氮雜菲(phen)、2,2'-聯口比啶 (bipy)、N,N'-二甲基乙二胺 (dmen);(2) [Cu(naag)(N)],N 為口比啶 (py)、3-甲基口比啶 (3Mpy)、4-甲基口比啶 (4Mpy)、4-胺基口比啶 (4apy)、4-二甲胺基口比啶(4dMapy)、N-甲基咪唑 (NMIm)、咪唑 (ImH)、2-甲基咪唑(2MImH)、4-甲基咪唑 (4MImH)。利用元素分析,紅外線光譜,紫外光-可見光吸收光譜,電子順磁共振光譜,及 X-光結構解析方法,完成錯合物結構的鑑定及鍵結性質的探討。
目前已完成 X-光單晶結構解析二價銅錯合物有:
(l) [Cu(naag)(phen)(H2O)]3H2O
三斜晶系 (triclinic),空間群為P1,晶格常數 a=9.056(2)A,b=11.249(4)A,C=11.632(5)A,α=115.33(3)°,β=103.41(2)°,γ=94.09(2)°,體積為1022.3(7)A3,單位晶格有二個分子 (Z=2),精算值 R=0.041,Rw=0.046。
(2) [Cu(naagCH2CH#)(phen)(ClO4)]
三斜晶系 (triclinic),空間群為p1,晶格常數 a=90294(4)A,b=10.846(4)A,C=12.216(5)A,α=110.94(1)°,β=105.15(1)°,γ=96.30(1)°,體積為 1076.3(4)A3 單位晶格有二個分子 (Z=2),精算值 R=0.043,Rw=0.057。
由可見光光譜部分經高斯交疊解析後,確知軌域順序如下:
(1) [Cu(A)(NN)(H20)]:dxy>>dz2>dx2-y2, dxz>dyz
(2) [Cu(A)(NN)(Cl04)]:dxy>>dz2>dx2-y2, dxz>dyz
(3) [Cu(A)(N)]:dx2-y2>>dz2>dxy>dyz>dxz
Copper(Ⅱ) complexes of two types, (l) [Cu(A)(NN)(H20)] and [Cu(A)(NN)(Cl04)]; (2) [Cu(A)(N)], where A=N-acetoacetylglycinate(naag); NN=1,10-phenanthroline(phen) , 2,2'-bipyridine (bipy) , N,N'-dimethylethylenediamine(dmen); N =pyridine(py), 3-methylpyridine(3Mpy), 4-methylpyridine (4Mpy), 4-aminopyridine (4apy), 4-dimethylaminopyridine (4dMapy), N-methylimidazole (NMIm), imidazole (ImH), 2-methylimidazole (2MlmH), 4-methylimidazole (4MImH), have been synthesized and characterized by elemental analyses, and IR, UV-VIS, and EPR spectroscopic measurements.
By single-crystal X-ray diffraction method, the crystal and molecular structures of [Cu(naag)(phen)(H20)]3H20, [Cu(naagCH2CH3)(phen)(CIO4)] have been determined. The crystal data of these two complexes are described below:
(1) [Cu(naag)(phen)(H20)]3H2O crystallizes in the triclinic, space group P1 with a=9.056(2)A, b=11.249(4)A, c=11.632(5)A, α=115.33(3)°, β=103.41(2)°, γ=94.09(2)°, V =1022.3(7)A3, Z=2, R=0.041, Rw=0.046.
(2) [Cu(naagCH2CH3)(phen)(Cl04)] crystallizes in the triclinic, space group P1 with a=9.249(4)A, b=10.846(4)A, c=12.216(5)A, α=110.94(1)°, β=105.15(1)°, γ=96.30(1)°, V =1076.3(4)A3, Z=2, R=0.043, Rw=0.057.
The solid state LF spectra of the complexes were deconvoluted into Gaussian component bands. The results were employed to interpret the electronic and bonding properties of the Cu(Ⅱ) complexes. In the meantime, the sequences of d orbitals were assigned as following:
(1) [Cu(A)(NN)(H2O)] dxy>>dz2>dx2-y2, dxz>dyz
(2) [Cu(A)(NN)(Cl04)] dxy>>dz2>dx2-y2, dxz>dyz
(3) [CU(A)(N)] dx2-y2>>dz2>dxy>dyz>dxz