本研究以二叔丁基環戊二烯基銅三苯基膦錯合物CptBu2CuPPh¬3 (1)為起始物。嘗試與疊氮化合物反應得到高價數的環戊二烯基銅的氮烯錯合物,由於溶解度問題無法有效純化而得到單一化合物。對於此化合物,我們利用CuAAC(Cu-catalyzed azide-alkyne cycloaddition)得到環化後的三唑衍伸物,先證明銅的存在。為了方便處理副產物的分離,希望可以得到CptBu2Cu(MeCN) 錯合物。我們將CptBu2CuPPh¬3 (1)在乙腈(MeCN)中迴流,但出現了乙腈環化反應的產物4-Amino-2,6-dimethyl pyrimidine (3)及其銅二聚體錯合物[4-Amino-2,6-dimethyl pyrimidine Cu]2 (2),並討論其銅-銅間距離與作用力。鑒於環化反應發生,我們拿苯乙炔(PhCCH)與CptBu2CuPPh¬3 (1)反應,但得到[CuPPh3-μ3-CCPh]4(4)四聚體。亦把CptBu2CuPPh¬3 (1)與三當量的2,6-xylCN(2,6-xylCN =2,6-dimethyl phenyl isocyanide) 加熱,環化了2,6-xylCN得到[(2,6-xylNC)2Cu(PPh3)2][Cu(indol)2] (5) indol= (7-methyl-1H-indol-1-yl)。當CptBu2CuPPh¬3 (1)與單電子氧化劑AgOTf得到[PPh3CuOTf]2(6)二聚體。
This research focuses in the reactivity studies of ditertbutylcyclopentadienyl copper triphenylphosphine complex (CptBu2CuPPh¬3, 1). In pursuit of higher oxidation state Cu species such as nitrene or carbine complexes, CptBu2CuPPh¬3 was treated with mesityl azide (MesN3). Due to the similar solubility, we couldn’t separate the targeted copper nitrene complex from the mixture products containing by-product, MesN=PPh3. We then proved the existence of copper via Cu-catalyzed azide-alkyne cycloaddition (CuAAC). In order for easier separation from byproducts, we attempted to synthesize the acetonitrile substituted complex CptBu2Cu(MeCN). Refluxing of complex (1) in acetonitrile however afforded 4-Amino-2,6-dimethyl pyrimidine (3) and a dimeric copper complex [4-Amino-2,6-dimethyl pyrimidine Cu]2 (2), which shows a close Cu-Cu contact of 2.49 Å. We then tested phenyl acetylene (PhCCH) to confirm if complex (1) also catalyzes the cycloaddition reactions. Unfortunately, we obtained the deprotonated phenyl acetylene product, [CuPPh3-μ3-CCPh]4 (4) tetramer. In addition, CptBu2CuPPh¬3 (1) reacted with 3 equiv. of 2,6-xylCN (2,6-xyl = 2,6-dimethylphenyl) at 85 oC, resulting in the formation of [(2,6-xylNC)2Cu(PPh3)2][Cu(indol)2] (5) [indol = (7-methyl-1H-indol-1-yl)]. Finally, we obtained a [PPh3CuOTf]2(6) dimer upon oxidation of CptBu2CuPPh¬3 (1) with AgOTf.