銅蛋白質模型錯合物研究:含N,N-雙(1,5-二甲基咪唑-4-甲基)-4'-甲苯胺之銅錯合物的合成、結構及性質研究

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2003

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為瞭解血青素的活性中心如何與氧氣進行可逆反應,本研究合成了一個含雙咪唑的三牙基配子:N,N-雙(1,5-二甲基咪唑-4-甲基)-4'-甲苯胺(bmiMemt),期望能在室溫下合成出穩定的血青素模型錯合物。 首先以此三牙基成功的合成一系列的二價銅錯合物:[Cu(bmiMemt)(bipy)(H2O)](ClO4)2(H2O)、[Cu(bmiMemt)(phen)](ClO4)2(H2O)、[Cu(bmiMemt)Br2](H2O)、[Cu(bmiMemt)(CH3COO)2](H2O)4.5、[Cu(bmiMemt)(Cl)](ClO4)(H2O)及[Cu(bmiMemt)2](ClO4)2(H2O)2,其中bipy為2,2'-聯吡啶,phen為1,10-二氮雜菲,再利用元素分析、紅外線光譜、電子吸收光譜及電子順磁共振光譜等,完成錯合物的鑑定及鍵結性質的探討。目前已完成X-光單晶結構解析的二價銅錯合物有: (1)fac-[Cu(bmiMemt)(bipy)(H2O)](ClO4)2 屬於斜方晶系(Orthorhombic),空間群為Pbca,晶格常數a=14.4325(2) Å,b=14.0859(3) Å,c=34.1018(6) Å;α=β=γ=90.00°,每單位晶格內含有8個分子(Z=8),精算值R=0.076,Rw=0.138。 (2)fac-[Cu(bmiMemt)(phen)](ClO4)2(CH3CN) 屬於單斜晶系(Monoclinic),空間群為Cc,晶格常數a=7.5940(2) Å,b=40.677(1) Å,c=11.7952(3) Å;α=γ=90.00°,β=99.368(2)°,每單位晶格內含有4個分子(Z=4),精算值R=0.0748,Rw=0.1853。 (3)mer-[Cu(bmiMemt)Br2] 屬於單斜晶系(Monoclinic),空間群為P21/n,晶格常數a=10.2466(2) Å,b=14.3563(3) Å,c=15.1856(2) Å;α=γ=90.00°,β=107.6543(9)°,每單位晶格內含有4個分子(Z=4),精算值R=0.050,Rw=0.085。 (4)mer-[Cu2(bmiMemt)2(CH3COO)3](OH)(H2O)3 屬於三斜晶系(Triclinic),空間群為P¯1,晶格常數a=9.3434(2) Å,b=17.6126(3) Å,c=19.0486(4) Å;α=94.2313(6)°,β=95.8050(7)°,γ=100.0088(7)°,每單位晶格內含有2個分子(Z=2),精算值R=0.101,Rw=0.231。 (5)mer-[Cu(bmiMemt)(Cl)](ClO4) 屬於單斜晶系(Monoclinic),空間群為P21/n,晶格常數a=7.0070(1) Å,b=22.9522(5) Å,c=14.4161(3) Å;α=γ=90.00°,β=97.952(1)°,每單位晶格內含有4個分子(Z=4),精算值R=0.064,Rw=0.114。 (6)cis-fac-[Cu(bmiMemt)2](ClO4)2 屬於單斜晶系(Monoclinic),空間群為C2/c,晶格常數a=20.580(2) Å,b=15.857(1) Å,c=27.262(2) Å;α=γ=90.00°,β=103.099(1)°,每單位晶格內含有8個分子(Z=8),精算值R=0.1040,Rw=0.2134。 將配子bmiMemt之一價銅錯合物,於室溫下與氧氣進行反應,以電子吸收光譜判斷反應產物,初步推測為μ-η2:η2-peroxodicopper(II)和bis(μ-oxo)dicopper(III)錯合物的混合物。並以2,4-二-特-丁基苯酚為受質,在室溫下進行酪胺酸酶模型系統的反應實驗,結果顯示2,4-二-特-丁基苯酚被氧化形成3,5-二-特-丁基鄰苯醌及3,3',5,5'-四-特-丁基-2,2'-聯苯酚,因此推斷此配子之一價銅錯合物在室溫下與氧氣反應,確實有形成μ-η2:η2-peroxo鍵結模式的錯合物,並具有酪胺酸酶的催化能力。
In order to reveal the oxygen-carrying properties of hemocyanin, a tridentate ligand, N,N-bis(1,5-dimethylimidazolyl-4-methyl)-4'-toluidine(bmiMemt), has been synthesized and characterized. A series of mixed ligand copper(II) complexes of N,N-bis(1,5- dimethylimidazolyl-4-methyl)-4'-toluidine, [Cu(bmiMemt)(bipy)(H2O)](ClO4)2(H2O), [Cu(bmiMemt)(phen)](ClO4)2(H2O), [Cu(bmiMemt)Br2](H2O), [Cu(bmiMemt)(CH3COO)2](H2O)4.5, [Cu(bmiMemt)(Cl)](ClO4)(H2O) and [Cu(bmiMemt)2](ClO4)2(H2O)2, where bipy=2,2'-bipyridine and phen=1,10-phenanthroline, have been successfully synthesized and characterized by elemental analysis, and infrared, electronic absorption, and EPR spectroscopic measurements. Six complexes have been characterized by single crystal X-ray diffraction analysis: (1)fac-[Cu(bmiMemt)(bipy)(H2O)](ClO4)2 Orthorhombic, space group Pbca with a=14.4325(2) Å, b=14.0859(3) Å, c=34.1018(6) Å;α=β=γ=90.00°;Z=8, R=0.076, Rw=0.138。 (2)fac-[Cu(bmiMemt)(phen)](ClO4)2(CH3CN) Monoclinic, space group Cc with a=7.5940(2) Å, b=40.677(1) Å, c=11.7952(3) Å;α=γ=90.00°, β=99.368(2)°;Z=4, R=0.0748, Rw=0.1853。 (3)mer-[Cu(bmiMemt)Br2] Monoclinic, space group P21/n with a=10.2466(2) Å, b=14.3563(3) Å, c=15.1856(2) Å;α=γ=90.00°, β=107.6543(9)°;Z=4, R=0.050, Rw=0.085。 (4)mer-[Cu2(bmiMemt)2(CH3COO)3](OH)(H2O)3 Triclinic, space group P¯1 with a=9.3434(2) Å, b=17.6126(3) Å, c=19.0486(4) Å;α=94.2313(6)°, β=95.8050(7)°, γ=100.0088(7)°;Z=2, R=0.101, Rw=0.231。 (5)mer-[Cu(bmiMemt)(Cl)](ClO4): Monoclinic, space group P21/n with a=7.0070(1) Å, b=22.9522(5) Å, c=14.4161(3) Å;α=γ=90.00°, β=97.952(1)°;Z=4, R=0.064, Rw=0.114。 (6)cis-fac-[Cu(bmiMemt)2](ClO4)2: Monoclinic, space group C2/c with a=20.580(2) Å, b=15.857(1) Å, c=27.262(2) Å;α=γ=90.00°, β=103.099(1)°;Z=8, R=0.1040, Rw=0.2134。 Based on the electronic spectral data, the reaction of [Cu(bmiMemt)]+ complex with oxygen likely results in the formation of a mixture of μ-η2:η2-peroxodicopper(II) and bis(μ-oxo)dicopper(III) complexes. Preliminary studies on tyrosinase modelling have been performed. The reaction of 2,4-di-tert-butylphenol and O2 catalyzed by [Cu(bmiMemt)]+ infers the formation of μ-η2:η2-peroxodicopper(II) complex, exhibiting tyrosinase-like activities.

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血青素, 模型錯合物, 酪胺酸酶, hemocyanin, model compound, tyrosinase

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