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• Main Authors: Shih-Fang Chen, 陳世芳
• Other Authors: 李光華
• Format: Others
• Language: zh-TW
• Published: 2014
• Online Access: http://ndltd.ncl.edu.tw/handle/45894906399282900175

碩士 === 國立中央大學 === 化學學系 === 102 === The C-N cross coupling catalyzed by NPh2H/ArI/CuI/1,10-Phenan- throline (phen)/MOtBu (M=Li, Na, K) system has been studied for many years. But the argument of Cu(I)-complex catalyst, which are [phen-Cu-NPh2] and M[Cu(NPh2)2], were still not stop. In order to clarify this argument, first we removed Phen to study Cu(I)-catalyzed mechanism. By density functional theory (DFT) studies, the proton transfer (PT) equilibrium, MOtBu + HNPh2 ⇌ MNPh2 + HOtBu, affects MNPh2 concentration, further the reaction rate is affected. Therefore, we directly used MNPh2/ArI/CuI system to remove the PT’s interferences, the result that the order of yield is LiNPh2 > NaNPh2 > KNPh2 corresponds with the oxidation-addition-activation-energy of M[Cu(NPh2)2], which were predicted our calculations. On the other hand, the calculated ligand exchange (LC) equilibrium, [Phen-Cu-NPh2] + MNPh2 ⇌ M[Cu(NPh2)2] + Phen, GLC, the results are GLC = -7.02 ~ -11.12 kcal/mol, which means that M[Cu(NPh2)2] is main species even if Phen is present. According to adding Phen accompanied decreasing yield in MNPh2/ArI/CuI/Phen experiments, this results breaking the myth of Phen enhanced reactivity.