酪胺酸酶之含氮硫三牙基二價銅錯合物的合成、結構及反應性之研究

Abstract

本研究使用兩個N2S三牙基的配位基，1,5-Bis(N-propylbenzimidazol-2-yl)-3-thiapentane (BBPrES)以及1,3-Bis(N-propylbenzimidazol-2-yl)-2-thiapropane (BBPrMS)，並且利用這兩個N2S三牙基的配子與水合過氯酸銅反應，得到三個五配位正二價銅錯合物，包含[Cu(BBPrES)(CH3CN)2](ClO4)2 (1)、 [Cu(BBPrMS)(CH3CN)(η1-ClO4)](ClO4) (2)、[Cu(BBPrES)(CH3CN)- (tBuCN)](ClO4)2 (3)。將錯合物1和錯合物3分別與丁醇鉀反應，分別得到雙核正二價銅錯合物[Cu2(BBPrES)2(OMe)2](ClO4)2 (4)和[Cu2(BBPrMS)2(OH)2](ClO4)2 (5)，五個錯合物皆得到X-光結構解析的晶體結構。我們以錯合物4及錯合物5在30ºC下催化2-萘酚的氧化反應，結果得到以dinol化合物的產物為主而不是binol的產物為主，產率分別為65%和74%。同時我們利用錯合物4及錯合物5在30ºC下催化3-羥基-2-萘甲酸甲酯進行氧化的反應，結果發現以雙苯環化合物的產物為主，產率皆為35%。

In this work, two N2S tridentate ligands, 1,5-Bis(N-propyl- benzimidazol-2-yl)-3-thiapentane (BBPrES) and 1,3-Bis- (N-propyl- benzimidazol-2-yl)-2-thiapropane (BBPrMS) were employed to synthesize a series of copper(II) complexes. Three five-coordinate mononuclear complexes of [Cu(BBPrES)(CH3CN)2](ClO4)2 (1), [Cu(BBPrMS)(CH3CN)(η1-ClO4)](ClO4) (2) and [Cu(BBPrES)(CH3CN)- (tBuCN)](ClO4)2 (3), were obtained by the reactions of copper(II) perchlorate hexahydrate with BBPrES or BBPrMS. Interestingly, the reactions of potassium tert-butoxide with complexes 1 and 2 in a methanol/tetrahydrofuran mixed solution lead gave a dicopper(II) to bis(μ-methanolato) complex (4), [Cu2(BBPrES)2(OMe)2](ClO4)2 and a dicopper(II) bis(μ-hydroxo) complex (5), [Cu2(BBPrMS)2(OH)2](ClO4)2. Complexes 1-5, were characterized by X-ray crystallography. Naphthalen-2-ol was selected to be the testing substrate for oxidative reaction catalyzed by complex 4 and 5 at 30ºC. The major product of the reaction was a dione compound 2'-hydroxy- 1,1'-binaphthalene-3,4-dione with a yield up to 65% and 74%, respectively. Only little product was observed. The product 2'-hydroxy- 1,1'-binaphthalene-3,4-dione was characterized by NMR and X-ray crystallography. Another substrate, we proceed methyl 3-hydroxy-2-naphthoate was also employed for oxidative reaction catalyzed by complex 4 and 5 at 30ºC. Confrastely, the major product of this substrate was binol in a yield of 35% for both reactions.