含銅蛋白質活性中心之擬態化合物研究— 含氮硫三牙基之一價錯合物之合成、結構及反應性探討
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2009
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為了模擬藍銅蛋白以及胜肽甘胺酸-羥化氧化酶(Peptidylglycine -hydroxylating monooxygenase，簡稱PHM)的活性中心，我們合成出兩個含氮硫之三牙配位基(BMIMS)與(MITMB)，並成功地合成出兩個具有BMIMS與MITMB的一價銅錯合物：[Cu2(BMIMS)2](CF3SO3)2 (1)和[Cu2(MITMB)2](CF3SO3)2 (4)。將錯合物1與硫醇鹽[SC6H4COO]2-、[SC6F5]-以及[SC6H4Si(CH3)3]-反應，其產物由核磁共振氫譜推測，有[Cu(BMIMS)SC6H4COO-]、[Cu(BMIMS)SC6F5]以及[Cu(BMIMS)SC6H4Si(CH3)3]的生成。將雙核結構的錯合物1和錯合物4與PPh3、CNC(CH3)3、CO等小分子反應則可形成一系列的單核錯合物：[Cu(BMIMS)PPh3](CF3SO3) (2)、[Cu(BMIMS)CNC(CH3)3](CF3SO3) (3)以及[Cu(MITMB)PPh3](CF3SO3) (5)，而[Cu(BMIMS)(CO)](CF3SO3)與[Cu(MITMB)(CO)](CF3SO3)分子的生成由IR光譜鑑定，顯示錯合物1與4都具有良好的反應性。並且藉由核磁共振光譜與IR光譜，得知配子BMIMS的供給電子能力是略強於MITMB。若將氧氣與錯合物1在甲醇/乙腈溶液下反應，以紫外-可見光光譜偵測該溶液可發現在兩組電荷轉移吸收峰在304 nm 、352 nm類似於Cu(II)-OOH錯合物的吸收光譜。
In order to mimic the active site of blue copper protein and peptidylglycine hydroxylating monooxygenase (PHM), we have synthesized two N2S(thioether) ligands, bis(4-methylimidazol-5-yl- methyl) sulfide (BMIMS) and 2-(4-Methylimidazol-5-ylmethyl)- thiomethyl-1-methylbenzoimidazole (MITMB). Two Cu(I) complexes of BMIMS and MITMB, [Cu2(BMIMS)2](OTf)2 (1) and [Cu2(MITMB)2]- (OTf)2 (4) have been successfully synthesized and fully characterized. We aimed to model the active site of the reduced form of blue copper protein by reacting complex 1 with thiosalicylic acid, pentafluoro- thiophenol and 2-(trimethylsilyl)benzenethiol, respectively. 1H-NMR spectra of the isolate products suggested the formation of [Cu(BMIMS)- SC6H4COO-], [Cu(BMIMS)SC6F5] and[Cu(BMIMS)SC6H4Si(CH3)3]. The dinuclear complexes 1 and 4 exhibit excellent reactivities toward small molecules, such as PPh3, CNC(CH3)3, and CO. Mononuclear Cu(I) complexes, [Cu(BMIMS)PPh3](OTf) (2), [Cu(BMIMS)CNC(CH3)3](OTf) (3) and [Cu(MITMB)PPh3](OTf) (5), were formed and structurally characterized, and [Cu(BMIMS)(CO)](OTf), [Cu(MITMB)(CO)](OTf) were characterized by IR. NMR and IR spectra illustrate that BMIMS is a stronger electron-donating ligand compared to MITMB. The reaction of dioxygen with complex 1 in a methanol/acetonitrile mixed solution monitored by UV-vis spectroscopy exhibited two charge transfer absorption bands at 304 nm and 352 nm . The UV-vis spectrum of the resulting species is similar to that of copper(II) hydroperoxide complexes.
In order to mimic the active site of blue copper protein and peptidylglycine hydroxylating monooxygenase (PHM), we have synthesized two N2S(thioether) ligands, bis(4-methylimidazol-5-yl- methyl) sulfide (BMIMS) and 2-(4-Methylimidazol-5-ylmethyl)- thiomethyl-1-methylbenzoimidazole (MITMB). Two Cu(I) complexes of BMIMS and MITMB, [Cu2(BMIMS)2](OTf)2 (1) and [Cu2(MITMB)2]- (OTf)2 (4) have been successfully synthesized and fully characterized. We aimed to model the active site of the reduced form of blue copper protein by reacting complex 1 with thiosalicylic acid, pentafluoro- thiophenol and 2-(trimethylsilyl)benzenethiol, respectively. 1H-NMR spectra of the isolate products suggested the formation of [Cu(BMIMS)- SC6H4COO-], [Cu(BMIMS)SC6F5] and[Cu(BMIMS)SC6H4Si(CH3)3]. The dinuclear complexes 1 and 4 exhibit excellent reactivities toward small molecules, such as PPh3, CNC(CH3)3, and CO. Mononuclear Cu(I) complexes, [Cu(BMIMS)PPh3](OTf) (2), [Cu(BMIMS)CNC(CH3)3](OTf) (3) and [Cu(MITMB)PPh3](OTf) (5), were formed and structurally characterized, and [Cu(BMIMS)(CO)](OTf), [Cu(MITMB)(CO)](OTf) were characterized by IR. NMR and IR spectra illustrate that BMIMS is a stronger electron-donating ligand compared to MITMB. The reaction of dioxygen with complex 1 in a methanol/acetonitrile mixed solution monitored by UV-vis spectroscopy exhibited two charge transfer absorption bands at 304 nm and 352 nm . The UV-vis spectrum of the resulting species is similar to that of copper(II) hydroperoxide complexes.
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含銅蛋白, 擬態化合物