多牙氮配位基金屬錯合物及其催化應用

Abstract

2,6-bis[bis(2-pyridylmethyl)-aminomethyl]-4-methylphenol(簡稱Hbpmp)是個含有兩個三牙氮的配位基，可以與不同的金屬形成具有雙金屬中心的錯合物。但是在文獻中只有對此配位基錯合物(如：Ni-Ni、Mn-Mn、FeII-FeIII、Zn-FeIII 等)的晶體和性質做討論，尚未有鈀金屬錯合物及其催化反應的研究，由於雙金屬中心的錯合物會使金屬在進行催化時有協和作用的可能性，於是本論文主要探討此配位基與二價鈀金屬形成的雙金屬錯合物的合成，以及金屬錯合物的催化反應。 Hbpm乃先以還原胺化反應合成出bis-(2-pyridylmethyl)amine(簡稱bpma)，再利用親核性取代反應將bpma接到2,6-bis(bromomethyl)-4-methylphenol上，即可得到具有兩個三牙基的Hbpmp，利用1H與13C NMR鑑定。鈀金屬錯合物可在常溫下將PdCl2(PhCN)2與Hbpmp溶於二氯甲烷溶液中反應一天，經由再沉澱得到，所得之錯合物可藉由1H NMR鑑定，並利用乙酸乙酯與甲醇混合溶液再結晶，得到其晶體結構。 利用所得到的鈀金屬錯合物進行Suzuki Coupling反應，可以在水中、低催化量下得到極高的產率。

2.6-bis[bis(2-pyridylmethyl)-aminomethyl]-4-methylphenol(Hbpmp) is a special ligand which containing two tri-dentate nitrogen binding sites, and can form bimetallic complexes with various metals. Until now, there are no catalytic applications of its metal complexes on catalysis, but only crystallography and characterization on the bimetallic species. It is expected that the two metal centers will have complementary interaction between each other. In this work, we have prepared the Pd(II)-Pd(II) complex and its catalytic application. The Pd(II)-Pd(II) complex could be formed by addition of PdCl2(PhCN)2 to Hbpmp in a dichloromethane solution. Upon recrystalization in a mixed EA and methanol solution, the desired complex was obtained in pure form, which was characterized by spectroscopic and X-ray structural analyses. Hbpmp can be prepared by using bis-(2-pyridylmethyl)amine and 2,6-bis(bromomethyl)-4-phenol undergo the nucleophilic substitution in THF solution. This Pd(II)-Pd(II) complex catalyzed the Suzuki coupling by a low-loading amount of catalyst, in water and short reaction time with great yields.